Fluorovinloxyacetamides, process for preparing same and herbicidal composition comprising same

ABSTRACT

Herbicidal fluorovinyloxyacetamide compounds of formula (I) are useful for protecting crops from weeds:                    
     wherein: 
     R 1  is a phenyl group optionally having one or more substituents selected from the group consisting of C 1-6  alkyl, halogen-substituted C 1-6  alkyl, C 1-6  alkoxy and halogen; 
     R 2  is a C 1-6  alkyl; or 
     R 1  and R 2  together with the nitrogen atom to which they are bound form a 5-, 6- or 7-membered nitrogen heterocycle optionally having one or more ring oxygen atoms, double bonds and C 1-6  alkyl substituents; 
     R 3  is a phenyl or thiophen-2-yl group optionally having one or more substituents selected from the group consisting of C 1-6  alkyl, halogen-substituted C 1-6  alkyl, C 1-6  alkoxy, methylenedioxy and halogen; and 
     R 4 is a perfluoro C 1-6  alkyl group.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of international application number PCT/KR99/00116, filed on Mar. 15, 1999, which is pending.

FIELD OF THE INVENTION

The present invention relates to novel fluorovinyloxyacetamides, a process for preparing same and a highly selective and effective herbicidal composition comprising same.

DESCRIPTION OF THE PRIOR ART

Due to the perpetual emergence of weeds resistant to the herbicide in use, there always exists a need to develop a new class of effective herbicides that can protect crops without harming the environment. For example, the sulfonylurea-based herbicides that have been widely used in controlling rice-field weeds for the last two decades have now become less effective, particularly in controlling annual weeds. Accordingly, many attempts have been made to develop new rice-field herbicides of different chemical classes, including those based on amides and carbamates.

There has recently been reported a new class of herbicides based on heteroaryloxyacetamide derivatives (DE Patent No. 2903966; DE Patent No. 3038636; DE Patent No. 3323334; DE Patent No. 3344236; DE Patent No. 3418167; DE Patent No. 3422861; DE Patent No. 440596; WO 95/34560; WO 96/08488; WO 96/11575; WO 96/28434; and WO 97/08160). However, these heteroaryloxyacetamides have limited herbicidal activity against a narrow spectrum of weeds.

SUMMARY OF THE INVENTION

Accordingly, it is a primary object of the present invention to provide a novel compound having superior herbicidal activity against a wide spectrum of weeds.

It is another object of the present invention to provide a process for the preparation of said compound.

It is a further object of the present invention-to provide a herbicidal composition comprising said compound.

In accordance with one aspect of the present invention, there is provided a novel fluorovinyloxyacetamide compound of formula (I):

wherein:

R¹ is a phenyl group optionally having one or more substituents selected from the group consisting of C₁₋₆ alkyl, halogen-substituted C₁₋₆ alkyl, C₁₋₆ alkoxy and halogen;

R² is a C₁₋₆ alkyl group; or

R¹ and R² together with the nitrogen atom to which they are bound form a 5-, 6- or 7-membered nitrogen heterocycle optionally having one or more ring oxygen atoms, double bonds and C₁₋₆ alkyl substituents;

R³ is a phenyl or thiophen-2-yl group optionally having one or more substituents selected from the group consisting of C₁₋₆ alkyl, halogen-substituted C₁₋₆ alkyl, C₁₋₆ alkoxy, methylenedioxy and halogen; and

R⁴ is a perfluoro C₁₋₆ alkyl group.

DETAILED DESCRIPTION OF THE INVENTION

The compound of formula (I) of the present invention may be in the form of the E isomer of formula (I-a), the Z isomer of formula (I-b), or a mixture thereof:

wherein R¹, R², R³ and R⁴ have the same meanings as defined in formula (I) above. The two stereoisomers, E and X isomers, are defined according to the terminology of the Cahn-Ingold-Prelog system(J. March, Advanced organic Chemistry, 3rd Ed., Wiley-Interscience) which is incorporated herein by way of reference.

Among the compounds of the present invention, preferred are: those wherein R¹ is a phenyl group optionally having a halogen, methyl or methoxy substituent, R² is a methyl or ipropyl group, R³ is a phenyl group optionally substituted with a halogen or methoxy group and R⁴ is CF₃ or CF₂CF₃; and those wherein R¹ and R² together with the nitrogen atom to which they are bound form a piperidino, hexamethyleneimino, morphorino or 1,2,3,6-tetrahydropyridino ring optionally having one or two C₁₋₂ alkyl substituents, R³ is a phenyl group optionally substituted with a halogen or methoxy group and R⁴ is CF₃.

The compound of the present invention may be prepared by reacting an alcoholic compound of formula (II) with a fluorovinyl compound of formula (III) in the presence of a base, as shown in Reaction Scheme A:

wherein R¹, R², R³ and R⁴ have the same meanings as defined in formula (I) above.

An alcoholic compound of formula (II) may be prepared by substitution, acetylation and hydrolysis of an amine of formula (VI) according to a conventional method(Hamm, P. C., J. Amer. Chem. Soc., 78, 2556 (1956); Hartman, W. W. et al., Org. Syn., Coll., 3, 650 (1955); and Brasen, W. R. et al., Org. Syn. Coll., 4, 582 (1963)), as shown in Reaction Scheme B:

wherein R¹ and R² have the same meanings as defined in formula (I) above.

A difluorovinyl compound of formula (III) may be prepared form a halogen compound of formula (VIII) by Grignard and Wittig reactions(Herkes, F. E. et al., J. Org. Chem., 32, 1311 (1967); and Wheaton, G. A. et al., J. Org. Chem., 48, 917 (1983)), as shown in Reaction Scheme C:

wherein X is Br or Cl; and R³ and R⁴ have the same meanings as defined in formula (I) above.

As shown in Reaction Scheme A, the fluorovinyloxyacetamide compound of the present invention may be prepared by reacting an alcoholic compound of formula (II) with a fluorovinyl compound of formula (III) in the presence of a base. Each of compounds of formula (II) and (III) may be used in equimolar amounts and the base may be used in one to two equivalent amounts. The base may be an inorganic base, e.g., sodium hydride, potassium hydride, potassium t-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate; or an organic base, e.g., triethylamine or pyridine. The solvent which may be used in the reaction is benzene, toluene, tetrahydrofuran, acetone, acetonitrile, dichloromethane, dimethylformamideor dimethylsulfoxide, individually or combined with water. The reaction may be conducted at a temperature ranging from room temperature to 100° C. The progress of the reaction is conveniently followed by measuring the disappearance of the compound of formula (II) with thin layer chromatography(TLC).

The compound of the present invention is obtained as a mixture of two isomers, i.e., the E and Z isomers.

For example, in the case of the compound of the present invention wherein R¹ is phenyl, R² is methyl, R³ is phenyl and R⁴ is CF₃(Compound 1), a 2:1 mixture of the Z and F isomers is obtained, the isomer ratio being determined on the basis of both ¹H-NMR and ¹⁹F-NMR analysis of the product. Namely, the peak area ratio of the ¹H-NMR peak for the methylene group of the Z isomer(a singlet at 4.30 ppm relative to CHCl₃) to that of E isomer(a singlet at 4.49 ppm) is about 2:1; and ¹⁹F-NMR analysis(reference compound: CFCl₃) shows a peak area ratio of about 2:1 when the peaks for the fluorine and CF₃ substituents of the Z isomer(a quartet having a coupling constant of 24.08 Hz at −84.99 ppm and a doublet having a coupling constant of 25.07 Hz at −57.36 ppm, respectively) are compared with those of the E isomer(a quartet having a coupling constant of 12.43 Hz at −83.40 ppm and a doublet having a coupling constant of 12.66 Hz at −57.95 ppm, respectively).

Likewise, the preparation of the compound of the present invention wherein R¹ and R² together with the nitrogen atom to which they are attached form a piperidino group, R³ is phenyl and R⁴ is CF₃(Compound 221) leads to a 2:1 mixture of the Z and E isomers. Namely, the peak area ratio of the 1H-NMR peak for the methylene group of the Z isomer(a singlet at 4.67 ppm) to that of the E isomer(a singlet 4.79 ppm) is about 2:1; and the ¹⁹F-NMR analysis(reference compound: CFCl₃) shows a peak area ratio of 2:1 when the peaks for the fluorine and CF₃ substituent of the Z isomer(a quartet having a coupling constant of 25.15 Hz at −84.28 ppm and a doublet having a coupling constant of 24.85 Hz at −57.38 ppm, respectively) are compared with those of the E isomer(a quartet having a coupling constant of 12.46 Hz at −82.24 ppm and a doublet having a coupling constant of 12.32 Hz at −57.83 ppm, respectively).

The compound of the present invention has herbicidal activity against a broad spectrum of weeds, in particular, against those belonging to the Gramineae family, e.g., rice(Oryza sativa L.), barnyardgrass(Echinochlora crus-galli 8P. BEAUV. var. oryzicola OHWI), bulrush(Scirpus juncoides ROXB), umbrellaplant(Cyperus difformis L.), flatsedge(Cyperus serotinus ROTTB), dayflower(Aneilema keisak HASSK), monochoria(Monochoria vaginalis PRESL), toothcup(Rotala indica KOEHE) and arrow head(Sagittaria pygmaea MIQ).

Accordingly, the present invention also includes within its scope a herbicidal composition comprising one or more of the compounds of formula (I) as an active ingredient, in association with herbicidally acceptable carriers.

The herbicidal composition of the invention may be formulated in various forms such as an emulsion, aqueous dispersion, powder and granules which may contain herbicidally acceptable carriers and additives. The compound of the formula (I) may be used in an amount of 10 to 90% on the basis of the weight of an emulsion or aqueous dispersion, 0.1 to 10% on the basis of the weight of powder, 1 to 30 % on the basis of the weight of granules.

Herbicidally acceptable carrier that may be used in the composition of the present invention is a liquid carrier, e.g., water, an alcohol(ethanol, ethylene glycol, glycerine), ketone(acetone, methylethylketone), ether(dioxane, tetrahydrofuran, cellosolve), aliphatic hydrocarbon(gasoline, Kerosene), halogenated hydrocarbon(chloroform, carbon tetrachloride), amide(dimethylformamide), ester(ethyl acetate, butyl acetate, fatty glycerine ester) and acetonitrile; and a solid carrier, e.g., mineral particle(Kaoline, clay, bentonite, dolomite, talc, silica, sand) and vegetable powder(shrubs).

The additive that may be used in the herbicidal composition of the present invention includes an emulsifier, adhesive, dispersion agent or permeating agent, e.g., nonionic, anionic or cationic interface active agent(fatty acid sodium salt, polyoxy alkyl ester, alkyl sulfonate ester). Further, an agrochemically active ingredient, e.g., an insecticide, fungicide, plant growth regulator, germicide, and fertilizer, may be added in the composition of the present invention.

The following Preparations and Examples are given for the purpose of illustration only and are not intended to limit the scope of the invention.

PREPARATION 1 Preparation of L-Methyl-2-hydroxyacetanilide(II)

Step 1: Preparation of N-Methyl-2-chloroacetanilide(V)

10.7 g(0.1 mol) of N-methylaniline(VI) was dissolved in 150 ml of dichloromethane containing 10.12 g(0.1 mol) of triethylamine, and 13.55 g(0.12 mol) of chloroacetylchloride was added dropwise thereto while cooling. The resulting solution was stirred at room temperature for 1 hour, and washed three times with water. The organic layer was dried and recrystallized in n-hexane to obtain 17.6 g(yield 96%) of the title compound as a yellowish brown solid.

¹H-NMR (CDCl₃, TMS) δ: 7.68-7.12(m, 5H), 3.92(s, 2H), 3.45(s, 3H); MS (m/e): 183(M⁺, 37), 134(51), 106(100), 90(52), 51(59). m.p.: 61-62° C.

Step 2 : Preparation of N-Methyl-2-acetoxyacetanilide(IV)

18.3 g(0.1 mol) of the compound obtained in Step 1 was added to 50 ml of dry dimethylformamide(DMF), and 9.8 g(0.12 mol) of sodium acetate was added thereto. The resulting solution was heated for 1 hour, cooled and 50 ml of water was added thereto. The resulting solution was extracted three times with ethyl acetate and the organic layer was dried. After removing the solvent, the residue was subjected to column chromatography using a mixture of n-hexane and ethyl acetate(9:1) as an eluent to obtain 19 g(yield 92%) of the title compound as a liquid.

¹H-NMR (CDCl₃, TMS) δ: 7.78-7.21(m, 5H), 4.48(s, 2H), 3.36(s, 3H), 2.21(s, 3H); MS (m/e): 207(M⁺, 8), 107(61), 77(30), 43(100).

Step 3: Preparation of N-Methyl-2-hydroxyacetanilide(II)

20.7 g(0.1 mol) of the compound obtained in Step 2 was added to 100 ml of methanol, and 4.8 g(0.12 mol) of sodium hydroxide was added slowly thereto. The resulting solution was refluxed with heating for 1 hour. The solvent was removed under a reduced pressure and 50 ml of water was added thereto. The resulting solution was extracted three times with ethyl acetate. The organic layer was dried, the solvent was removed and the residue was recrystallized in n-hexane to obtain 14 g(yield 85%) of the title compound as a white solid.

¹H-NMR (CDCl₃, TMS) δ: 7.54-7.15(m, 5H), 3.82(d, 2H), 3.38(t, 1H), 3.32(s, 3H); MS (m/e): 165(M⁺, 34), 134(41), 106(100), 77(81); m.p.: 41-42° C.

PREPARATIONS 2 to 31

The procedure of Preparation 1 was repeated to obtain compounds of formula (II) having various R¹ and R² groups, as in Table 1. The ¹H-NMR and MS analysis data and melting points of these compounds are also shown in Table 1. L in Table 1 represents liquid.

TABLE 1 (II)

Prep. No. R¹ R² state(° C.) NMR (CDCl₃, TMS) δ (ppm) MS (m/e) 1 C₆H₅ CH₃ 41˜42 7.54˜7.15(m, 5H), 3.82(d, 2H), 3.38(t, 1H), 3.32(s, 3H) 165(34), 134(41), 106(100), 77(81) 2 4-CH₃O—C₆H₄ CH₃ 78˜79 7.38˜6.88(m, 4H), 3.85(s, 3H), 3.81(d, 2H), 3.40(t, 1H), 195(42), 136(100), 122(58) 3.35(s, 3H) 3 4-F—C₆H₄ CH₃ 105˜106 7.36˜7.04(m, 4H), 3.80(d, 2H), 3.40(t, 1H), 3.31(s, 3H) 183(31), 152(45), 125(100), 95(28) 4 4-Cl-C₆H₄ CH₃ 80˜81 7.54˜7.05(m, 4H), 3.84(d, 2H), 3.37(t, 1H), 3.34(s, 3H) 199(41), 168(39), 140(100), 45(54) 5 2, 4-F₂—C₆H₃ CH₃ 117˜118 7.12˜6.78(m, 3H), 4.35(b, 1H), 3.82(s, 2H), 3.29(s, 3H) 201(46), 170(42), 142(100), 59(82) 6 2, 4-Cl₂—C₆H₃ CH₃ 58˜59 7.67˜7.08(m, 3H), 3.81(d, 2H), 3.39(t, 1H), 3.38(s, 3H) 233(23), 198(100), 174(79) 7 C₆H₅ C₂H₅ 38˜39 7.56˜7.02(m, 5H), 3.88(q, 2H), 3.83(d, 2H), 3.42(t, 1H), 179(21), 120(100), 106(73), 77(87) 1.20(t, 3H) 8 4-CH₃-C₆H₄ C₂H₅ 63˜64 7.28˜6.96(m, 4H), 3.78(q, 2H), 3.72(d, 2H), 3.42(t, 1H), 193(47), 162(37), 134(100), 2.36(s, 3H), 1.12(t, 3H) 120(68), 91(50) 9 4-CH₃O-C₆H₄ C₂H₅ 53˜54 7.38˜6.78(m, 4H), 3.86(s, 3H), 3.84(q, 2H), 3.83(d, 2H), 209(77), 150(100), 136(78) 3.50(t, 1H), 1.18(t, 3H) 10 3-CF₃-C₆H₄ C₂H₅ L 7.95˜7.20(m, 4H), 3.95(q, 2H), 3.80(d, 2H), 3.51(t, 1H), 247(31), 188(100), 174(92), 1.18(t, 3H) 145(47) 11 2-Cl-C₆H₄ C₂H₅ 47˜48 7.75˜7.05(m, 4H), 4.13(m, 1H), 3.82(m, 1H), 3.76(d, 2H), 213(26), 178(100), 154(42), 3.48(t, 1H), 1.20(t, 3H) 140(42) 12 3-Cl-C₆H₄ C₂H₅ L 7.51˜6.95(m, 4H), 3.86(q, 2H), 3.83(d, 2H), 3.53(t, 1H), 213(38), 182(57), 154(100), 1.20(t, 3H) 140(79) 13 4-Cl—C₆H₄ C₂H₅ 111˜112 7.62˜7.00(m, 4H), 3.86(q, 2H), 3.84(d, 2H), 3.55(t, 1H), 213(36), 154(100), 140(84) 1.23(t, 3H) 14 C₆H₅ n-C₃H₇ 58˜59 7.62˜6.98(m, 5H), 3.86(t, 2H), 3.80(d, 2H), 3.45(t, 1H), 193(23), 151(44), 106(100), 77(53) 1.85˜1.20(m, 2H), 1.20(t, 3H) 15 4-CH₃O—C₆H₄ n-C₃H₇ 40˜41 7.16˜6.85(m, 4H), 3.84(s, 3H), 3.71(d, 2H), 3.65(t, 2H), 223(63), 150(40), 136(100), 43(47) 3.46(t, 1H), 1.63-1.46(m, 2H), 0.90(t, 3H) 16 C₆H₅ i-C₃H₇ 42˜43 7.48-6.88(m, 5H), 5.05˜4.65(m, 1H), 3.64(d, 2H), 193(24), 120(100), 77(52), 3.52(t, 1H), 1.02(d, 6H) 43(100) 17 2-CH₃—C₆H₄ i-C₃H₇ L 7.48˜6.98(m, 4H), 5.12˜4.64(m, 1H), 3.62(d, 2H), 207(47), 134(100), 45(89) 3.34(t, 1H), 2.37(s, 3H), 1.28(d, 3H), 1.00(d, 3H) 18 3-CH₃—C₆H₄ i-C₃H₇ 51˜52 7.49˜6.85(m, 4H), 5.15˜4.72(m, 1H), 3.72(d, 2H), 207(48), 134(94), 91(72), 45(100) 3.55(t, 1H), 2.48(s, 3H), 1.08(d, 6H) 19 3-CH₃O—C₆H₄ i-C₃H₇ L 7.41˜6.61(m, 4H), 5.08˜4.84(m, 1H), 3.84(s, 3H), 223(18), 15O(100), 84(26), 45(38) 3.69(d, 2H), 3.57(t, 1H), 1.08(d, 6H) 20 4-CH₃O—C₆H₄ i-C₃H₇ 96˜97 7.32˜6.78(m, 4H), 5.25˜4.76(m, 1H), 3.86(s, 3H), 223(27), 181(47), 150(100), 3.68(d, 2H), 3.51(t, 1H), 1.10(d, 6H) 123(79), 107(65), 45(54) 21 3-CF₃—C₆H₄ i-C₃H₇ 48˜49 7.87˜7.21(m, 4H), 5.18˜4.86(m, 1H), 3.76(d, 2H), 261(26), 188(63), 43(100) 3.51(t, 1H), 1.08(d, 6H) 22 4-F—C₆H₄ i-C₃H₇ 52˜53 7.21˜7.03(m, 4H), 5.08˜4.86(m, 1H), 3.61(d, 2H), 211(20), 138(100), 95(33), 43(86) 3.45(t, 1H), 1.07(d, 6H) 23 2-Cl—C₆H₄ i-C₃H₇ 67˜68 7.78˜7.23(m, 4H), 5.16˜4.85(m, 1H), 3.78(d, 2H), 227(8), 192(69), 154(83), 45(100) 3.50(t, 1H), 1.35(d, 3H), 1.20(d, 3H) 24 3-Cl—C₆H₄ i-C₃H₇ 62˜63 7.58˜6.95(m, 4H), 5.15˜4.85(m, 1H), 3.80(d, 2H), 227(27), 154(100), 43(76) 3.54(t, 1H), 1.08(d, 6H) 25 2-Cl-4-F—C₆H₃ i-C₃H₇ 51˜52 7.51˜7.15(m, 3H), 5.14˜4.87(m, 1H), 3.78(d, 2H), 245(19), 210(24), 172(28), 43(100) 3.48(t, 1H), 1.32(d, 3H), 1.15(d, 3H) 26 3,4-Cl₂—C₆H₃ i-C₃H₇ 67˜68 7.72˜6.97(m, 3H), 5.12˜4.84(m, 1H), 3.75(d, 2H), 261(36), 188(28), 45(100) 3.46(t, 1H), 1.16(d, 6H) 27 3-CH₃—C₆H₄ CH₃ L 7.42˜6.84(m, 4H), 3.82(d, 2H), 3.41(t, 1H), 3.32(s, 3H), 179(61), 120(100), 59(67) 2.37(s, 3H) 28 4-CH₃—C₆H₄ CH₃ 58 7.38˜6.87(m, 4H), 3.81(d, 2H), 3.38(t, 1H), 3.31(s, 3H), 179(47), 120(100), 59(86) 2.35(s, 3H) 29 3,4- CH₃ 80 7.37˜6.84(m, 3H), 3.82(d, 2H), 3.36(t, 1H), 3.33(s, 3H), 193(57), 134(100) (CH_(3‘)) _(2‘—C) ₆H₃ 2.25(s, 6H) 30 3-Cl—C₆H₄ CH₃ 66 7.67˜7.01(m, 4H), 3.84(d, 2H), 3.53(t, 1H), 3.36(s, 3H) 199(58), 140(100), 75(82) 31 3,4- i-C₃H₇ L 7.43˜6.85(m, 3H), 5.32˜4.84(m, 1H), 3.70(d, 2H), 3.31(t, 1H), 221(61), 162(100), 59(48) (CH₃)₂—C₆H₃ 2.34(s, 6H), 1.18(d, 6H)

PREPARATION 32 Preparation of N-2-Hydroxyacetylpiperidine(II)

Step 1: Preparation of N-2-Chloroacetylpiperidine(V)

The procedure of Step 1 of Preparation 1 was repeated except that 8.5 g of piperidine was used in place of N-methylaniline and that column chromatography using a mixture of n-hexane and ethyl acetate(4:1) as an eluent was conducted in place of recrystallization to obtain 14.8 g(yield 92%) of the title compound as a yellowish brown liquid.

¹H-NMR (CDCl₃, TMS) δ: 4.08(s, 2H), 3.76-3.18(m, 4H), 1.98-1.21(m, 6H); MS (m/e): 161(M⁺, 26), 126(100), 69(37), 41(68).

Step 2: Preparation of N-2-Acetoxyacetylpiperidine(IV)

The procedure of Step 2 of Preparation 1 was repeated except that 16.1 g(0.1 mol) of the compound obtained in Step 1 was used and that column chromatography was conducted using a 4:1 mixture of n-hexane and ethyl acetate as an eluent to obtain 16.5 g(yield 89%) of the title compound as a liquid.

¹H-NMR (CDCl₃, TMS) δ: 4.67(s, 2H), 3.68-3.10(m, 4H), 2.12(s, 3H), 1.68-1.38(m, 6H); MS (m/e): 185(M⁺, 21), 112(51), 69(73), 43(100).

Step 3: Preparation of N-2-Hydroxyacetylpiperidine(II)

The procedure of Step 3 of Preparation 1 was repeated except that 18.5 g of the compound obtained in Step 2 was used and that column chromatography using a 2:1 mixture of n-hexane and ethyl acetate as an eluent was conducted in place of recrystallization to obtain 11.7 g(yield 82%) of the title compound.

¹H-NMR (CDCl₃, TMS) δ: 4.08(d, 2H), 3.97(t, 1H), 3.67-3.02(m, 4H), 1.75-1.15(m, 6H), MS (m/e): 143(M⁺, 35), 112(86), 69(77), 43(100).

PREPARATIONS 33 to 48

The procedure of Preparation 32 was repeated to obtain compounds of formula (II) having various R¹ and R² groups, as in Table 2. The ¹H-NMR and MS analysis data and melting points of these compounds are also shown in Table 2. L in Table 2 represents liquid.

TABLE 2 (II)

Prep. state No. R¹ R² (° C.) NMR (CDCl₃, TMS) δ (ppm) MS (m/e) 32 —(CH₂)₅— L 4.08(d, 2H), 3.97(t, 1H), 3.67˜3.02(m, 4H), 1.75˜1.15(m, 6H) 143(35), 112(86), 69(77), 43(100) 33 —CH(CH₃)(CH₂)₄— L 4.12(d, 2H), 3.85(t, 1H), 3.46˜2.67(m, 3H), 1.94˜1.46(m, 6H), 157(37), 126(72), 84(100), 55(66) 1.23(d, 3H) 34 —CH(CH₃CH₂)(CH₂)₄— L 4.13(d, 2H), 4.08(t, 1H), 3.45˜2.64(m, 3H), 1.85˜1.38(m, 8H), 171(16), 142(38), 84(100), 55(48) 0.86(t, 3H) 35 —CH(CH₃)(CH₂)₃ L 4.71(b, 1H), 4.15(d, 2H), 3.98˜3.54(m, 2H), 1.97˜1.46(m, 6H), 171(28), 98(97), 55(99), 41(100) CH(CH₃)— 1.25(d, 6H) 36 —(CH₂)₂CH═CHCH₂— 77˜78 5.86˜5.69(m, 2H), 4.16(d, 2H), 4.15(t, 1H), 3.75˜3.64(m, 2H), 141(39), 82(57), 67(86), 54(83), 41 3.30(t, 2H), 2.27˜2.05(m, 2H) (100) 37 —(CH₂)₂O(CH₂)₂— 52˜53 4.13(d, 2H), 3.80˜3.48(m, 8H), 3.41(1, 1H) 145(75), 100(67), 86(55), 42(100) 38 —(CH₂)₃C(C₄H₄)C— 78˜79 7.28˜7.03(m, 4H), 4.18(d, 2H), 3.80(t, 1H), 3.78˜3.54(m, 2H), 191(36), 132(100), 117(30), 77(49) 2.75(t, 2H), 1.98(t, 2H) 39 —(CH₂)₆— L 4.15(d, 2H), 3.84(t, 1H), 3.78˜3.12(m, 4H), 1.98˜1.28(m, 5H) 157(11), 126(72), 84(100), 47(79) 40 C₂H₅ C₂H₅ L 4.05(d, 2H), 3.78(t, 1H), 3.48(q, 2H), 3.23(q, 2H), 1.15(t, 6H) 131(25), 100(71), 72(100), 44(86) 41 n-C₃H₇ n-C₃H₇ L 4.06(d, 2H), 3.80(t, 1H), 3.42(q, 2H), 3.15(q, 2H), 1.85˜1.15 159(23), 86(29), 72(100), 43(94) (m, 4H), 0.97(t, 6H) 42 i-C₃H₇ i-C₃H₇ 63˜64 4.08(d, 2H), 3.95(t, 1H), 3.84˜3.35(m, 2H), 1.42(d, 6H), 1.28 159(45), 128(36), 86(94), 43(100) (d, 6H) 43 CH₂═CHCH₂ CH_(2‘═) L 6.12˜5.02(m, 6H), 4.12(d, 2H), 4.01˜3.94(m, 4H), 3.65(t, 1H) 155(36), 124(27), 56(37), 41(100) CHCH₂ 44 n-C₄H₉ n-C₄H₉ L 4.14(d, 2H), 3.72(t, 1H), 3.36(t, 4H), 1.64˜1.19(m, 8H), 187(21), 86(57), 57(100), 44(58) 0.96(t, 6H) 45 i-C₄H₉ i-C₄H₉ L 4.12(d, 2H), 3.74(t, 1H), 3.24(d, 4H), 2.13˜1.78(m, 2H), 187(44), 144(31), 86(100), 57(69) 0.87(d, 12H) 46 C₂H₅ i-C₃H₇ L 4.14(d, 2H), 3.81(t, 1H), 3.75˜3.56(m, 1H), 3.27(q, 2H), 145(11), 86(38), 72(97), 43(100) 1.18(d, 6H), 1.15(t, 3H) 47 CH₃ n-C₄H₉ L 4.08(d, 2H), 3.79(t, 1H), 3.45(t, 2H), 2.85(s, 3H), 1.78˜1.08 145(12), 114(21), 57(41), 44(100) (m, 4H), 0.98(t, 3H) 48 CH₃ C₆H₅CH₂ L 7.25˜7.09(m, 5H), 5.45(t, 1H), 4.58(s, 2H), 4.38(d, 2H), 179(48), 120(87), 59(100) 2.98(s, 3H)

PREPARATION 49 Preparation of 2,2-Difluoro-1-trifluoromethyl-4′-methoxy styrene(III)

Step 1: Preparation of 2,2,2-Trifluoromethyl-4′-methoxyphenylketone(VII)

5.1 g(0.21 g atom) of magnesium was placed in 300 ml of dry diethyl ether and 37.4 g(0.2 mol) of p-bromoanisole was added dropwise thereto under a nitrogen atmosphere to prepare a Grignard reagent. The Grignard reagent solution was cooled to −78° C. and 28.4 g(0.2 mol) of ethyl trif luoroacetate was added dropwise thereto. The resulting solution was stirred for 30 to 60 minutes, mixed with crushed ice, acidified with concentrated hydrochloric acid and then extracted three times with diethyl ether. The organic layer was dried over magnesium sulfate and the solvent was removed under a reduced pressure to obtain a residue. The residue was distilled at 72 to 73° C./20 mmHg to obtain 35.09 g (yield 86%) of the title compound as a colorless oil.

¹H-NMR (CDCl₃, TMS) δ: 7.62-6.81(m, 4H), 3.86(s, 3H); MS (m/e): 204(M⁺, 56), 135(100), 107(86), 92(66), 77(92).

Step 2: Preparation of 2,2-Difluoro-1-trifluoromethyl-4′-methoxy Styrene(III)

26.2 g(0.1 mol) of triphenylphosphine was dissolved in 250 ml of dry THF and 25.2 g(0.12 mol) of dibromodifluoromethane was added dropwise thereto under a nitrogen atmosphere at a temperature below 10° C. The resulting solution was stirred for thirty minutes and 10.2 g(0.05 mol) of the compound obtained in Step 1 was added thereto. The resultant solution was refluxed for 12 hours, cooled and distilled under a reduced pressure. The product was redistilled at 72 to 74° C. at 10 mmHg to obtain 9.36 g(yield 78.7%) of the title compound as a colorless liquid.

¹H-NMR (CDCl₃, TMS) δ: 7.48-6.79(m, 4H), 3.79(s, 3H); MS (m/e): 238(M⁺, 69), 195(14), 145(35), 74(33), 59(100).

PREPARATIONS 50 to 65

The procedure of Preparation 49 was repeated to obtain compounds of formulas (VII) and (III) having various R³ and R⁴ groups, as in Tables 3a and 3b, respectively. The ¹H-NMR and MS analysis data and melting points of these compounds are also shown in respective tables.

PREPARATION 66 Preparation of 2,2-Difluoro-1-pentafluoroethyl styrene(III)

The procedure of Preparation 49 was repeated except that bromobenzene and ethyl pentaf luoropropionate were used in place of bromoanisole and ethyl trifluoroacetate, respectively, to obtain the title compound. The ¹H-NMR and MS analysis data and melting points of the compounds of formulas (VII) and (III) are also shown in Tables 3a and 3b, respectively.

TABLE 3a (VII)

Prep. Nos. 49-65: R⁴ = CF₃ Prep. No. 66: R⁴ = CF₂CF₃ Prep. No. R³ ¹H-NMR(CDCl₃, TMS) δ (ppm) MS (m/e) yield (%) b.p. (mmHg) 49 4-CH₃O—C₆H₄— 7.62˜6.81(m, 4H), 3.86(s, 3H) 204(56), 135(100), 107(86), 92(66), 77(92) 86 72˜73 (20) 50 3-CH₃—C₆H₄— 7.52˜6.92(m, 4H), 2.25(s, 3H) 188(16), 135(45), 119(96), 91(100), 65(45) 61 70˜71 (20) 51 4-CH₃—C₆H₄— 7.42˜6.92(m, 4H), 2.25(s, 3H) 188(12), 119(100), 91(96), 65(45) 68 65˜66 (8) 52 4-C₂H₃—C₆H₄— 7.46˜7.19(m, 4H), 2.68(q, 2H), 1.23(t, 3H) 202(40), 133(91), 105(100), 76(64) 62 column 53 3,4-(CH₃)₂—C₆H₃— 7.52˜6.69(m, 3H), 2.23(s, 3H), 2.20(s, 3H) 202(43), 133(98), 69(100) 71 column 54 3,5-(CH₃)₂—C₆H₃— 7.31˜7.01(m, 3H), 2.25(s, 6H) 202(24), 133(100), 69(24) 69 column 55 3-CH₃O—C₆H₄— 7.41˜6.79(m, 4H), 3.79(s, 3H) 204(36), 135(100), 107(56), 77(94) 78 64˜65 (33) 56 C₆H₃— 7.52˜7.12(m, 5H) 174(21), 105(100), 77(82), 69(54) 71 64˜65 (33) 57 4-C₂H₃O—C₆H₄— 7.54˜6.76(m, 4H), 4.09(q, 2H), 1.32(t, 3H) 218(16), 149(88), 121(62), 76(100) 69 column 58 3,4-OCH₂O—C₆H₄— 7.92˜7.43(m, 3H), 6.25˜6.01(s, 2H) 218(42), 149(100), 65(49) 73 column 59 3-CF₃—C₆H₄— 8.60˜7.61(m, 4H) 242(10), 173(68), 145(100), 76(62) 67 column 60 3-F—C₆H₄— 7.56˜6.89(m, 4H) 192(25), 123(100), 95(78), 75(31) 54 59˜60 (30) 61 4-F—C₆H₄— 7.76˜6.92(m, 4H) 192(16), 169(54), 123(100), 95(91), 75(76) 59 66˜67 (34) 62 3-Cl—C₆H₄— 8.38˜7.45(m, 4H) 208(10), 139(93), 111(100), 75(64) 70 58˜59 (10) 63 4-Cl—C₆H₄— 7.51˜7.41(m, 4H) 208(100), 173(92), 97(54), 69(24) 61 83˜84 (24) 64 3,5-Cl₂—C₆H₃— 8.12˜7.86(m, 3H) 242(55), 173(100), 145(64), 109(32) 45 75˜76 (4) 65 C₄H₃S-2-yl- 8.28˜7.28(m, 3H) 180(23), 111(45), 84(100) 76 column 66 C₆H₅ 7.48˜7.02(m, 5H) 224(48), 205(100), 119(75) 68 62˜63(22)

TABLE 3b (III)

Prep. Nos. 49-65: R⁴ = CF₃ Prep. No. 66: R⁴ = CF₂CF₃ Prep. No. R³ ¹H-NMR(CDCl₃, TMS) δ (ppm) MS (m/e) yield (%) b.p. (mmHg) 49 4-CH₃O—C₆H₄— 7.48˜6.79(m, 4H), 3.79(s, 3H) 238(69), 195(14), 145(35), 74(33), 59(100) 79 72˜74 (10) 50 3-CH₃—C₆H₄— 7.46˜6.98(m, 4H), 2.43(s, 3H) 222(20), 203(70), 134(100) 45 column 51 4-CH₃—C₆H₄— 7.32˜7.18(m, 4H), 2.45(s, 3H) 222(64), 203(23), 134(100) 62 column 52 4-C₂H₃—C₆H₄— 7.38˜7.25(m, 4H), 2.68(q, 2H), 1.19(t, 3H) 236(20), 145(100), 90(54) 62 column 53 3,4-(CH₃)₂—C₆H₄— 7.28˜7.02(m, 3H), 2.38(s, 3H), 2.32(s, 3H) 236(18), 84(33), 45(100) 78 column 54 3,5-(CH₃)₂—C₆H₄— 7.32˜7.12(m, 3H), 2.41(s, 6H) 236(29), 217(65), 148(100), 45(92) 98 column 55 3-CH₃O—C₆H₄— 7.48˜6.87(m, 4H), 3.81(s, 3H) 238(42), 207(45), 188(37), 139(100), 69(94) 54 75 (10) 56 C₆H₃— 7.59˜7.31(m, 5H) 208(48), 84(83), 43(100) 67 column 57 4-C₂H₅O—C₆H₄— 7.51˜6.85(m, 4H), 4.12(q, 2H), 1.29(t, 3H) 252(47), 233(100), 84(64) 73 column 58 3,4-OCH₂O—C₆H₄— 7.01˜6.79(m, 3H), 6.01(s, 2H) 252(46), 233(63), 164(82), 69(100) 72 column 59 3-CF₃—C₆H₄— 7.82˜7.18(m, 4H) 276(52), 257(92), 188(100) 52 column 60 3-F—C₆H₄— 7.53˜6.96(m, 4H) 226(52), 207(25), 54(100) 54 column 61 4-F—C₆H₄— 7.52˜6.83(m, 4H) 226(20), 84(100) 63 column 62 3-Cl—C₆H₄— 7.54˜7.23(m, 4H) 242(26), 223(72), 188(49), 169(100) 63 column 63 4-Cl—C₆H₄— 7.56˜7.21(m, 4H) 242(35), 207(25), 174(70), 139(100), 60(79) 45 58 (10) 64 3,5-Cl₂—C₆H₅— 7.57˜7.19(m, 3H) 276(100), 241(45) 84 85 (10) 65 C₄H₃S-2-yl- 7.67˜6.92(m, 3H) 214(42), 195(92), 126(100), 47(86) 63 column 66 C₆H₅ 7.57˜6.89(m, 5H) 246(67), 227(57), 127(100), 119(35) 48 138˜139(737)

EXAMPLE 1 Preparation of N-Methyl-(2′-fluoro-1′-trifluoromethylstyryl-2′-oxy)acetanilide (Compound 1)

330 mg(2 mmol) of N-methyl-2-hydroxyacetanilide obtained in Preparation 1 was added to 10 ml of acetone and 0.22 ml of lOM sodium hydroxide solution(2.2 mmol) was added thereto. The resulting solution was stirred for 30 minutes and 416 mg(2 mmol) of 2,2-difluoro-1-trifluoromethyl styrene obtained in Preparation 56 was added slowly thereto. The resultant solution was stirred for 1 to 2 hours. Acetone was removed under a reduced pressure and the resulting solution was mixed with water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and the solvent was removed under a reduced pressure. The residue was subjected to silica gel column chromatography using a mixture of n-hexane and ethyl acetate (9:1) as an eluent to obtain 655 mg(yield 92.8%) of the title compound having two isomers as a colorless liquid. 1H-NMR (CDCl₃TMS) δ: 7.52-6.91(m, 10H), 4.49(E isomer) 4.30(Z isomer)(s, 2H), 3.30(s, 3H)

MS (m/e): 353(M⁺, 12), 177(42), 120(100), 91(72), 77(96) ¹⁹F-NMR (CDCl₃, CFCl₃) δ: −57.36(Z isomer) −57.95(E isomer)(d, 3F), −83.40(E, isomer) −84.99(Z isomer)(q, 1F)

EXAMPLE 2 Preparation of (E)-N-Methyl-(2′-fluoro-1′-trifluoromethylstyryl-2′-oxy)acetanilide (Compound 2)

The compound obtained in Example 1 was subjected to column chromatography using a mixture of n-hexane and ethyl acetate(9:1) as an eluent to isolate a pure form of the E isomer as a colorless solid.

E isomer; ¹H-NMR (CDCl₃, TMS) δ: 7.54-6.90(m, 10H), 4.49(s, 2H), 3.31(s, 3H); MS (m/e): 353(M⁺, 43), 177(48), 120(100), 91(68), 7(82); ¹⁹F-NMR (CDCl₃, CFCl₃) δ: −57.95(d, 3F), −83.40(q, 1F) m.p.: 91-92° C.

EXAMPLE 3 Preparation of (Z)-N-Methyl-(2′-fluoro-1′-trifluoromethylstyryl-2′-oxy)acetanilide (Compound 3)

The compound obtained in Example 1 was subjected to column chromatography using a mixture of n-hexane and ethyl acetate(9:1) as an eluent to isolate a pure form of the Z isomer as a colorless oil.

Z isomer; ¹H-NMR (CDCl₃, TMS) δ: 7.51-7.11(m, 10H), 4.30(s, 2H), 3.30(s, 3H); MS (m/e): 353(M⁺, 57), 177(40), 120(100), 91(70), 77(97); ¹⁹F-NMR (CDCl₃, CFCl₃) δ: −57.36(d, 3F), −84.99(q, 1F).

EXAMPLES 4 to 220

Using each of the alcoholic compounds obtained in Preparations 1 to 31 and each of the fluorovinyl compounds obtained in Preparations 49 to 66, the procedure of Example 1 was repeated to obtain 217 compounds(Compounds 4 to 220) of formula (I) of the present invention having various R¹, R², R³ and R⁴ groups listed in Table 4. The ¹H-NMR and MS data and melting points of these compounds are also shown in Table 4. L in Table 4 represents liquid.

TABLE 4 R⁴ = CF₃ (I)

Comp. No. R¹ R² R₃ state (° C.) NMR (CDCl₃, TMS) δ (ppm) MS (m/e) 1 C₆H₅ CH₃ C₆H₅ L 7.52˜6.91(m, 10H), 4.49(E) 4.30(Z) (s, 2H), 3.30(s, 3H) 353(12), 177(42), 120(100), 91(72), 77(96) 2 C₆H₅ CH₃ C₆H₅ 91-92 7.54˜6.90(m, 10H), 4.49(s, 2H), 3.31(s, 3H) 353(43), 177(48), 120(100), 91(68), 77(82) 3 C₆H₅ CH₃ C₆H₅ L 7.51˜7.11(m, 10H), 4.30(s, 2H), 3.30(s, 3H) 353(57), 177(40), 120(100), 91(70), 77(97) 4 C₆H₅ CH₃ 3-CH₃—C₆H₄ L 7.51˜6.98(m, 9H), 4.48(E) 4.31(Z) (s, 2H), 3.31(s, 3H), 367(45), 148(100), 120(54), 2.35(s, 3H) 91(37) 5 C₆H₅ CH₃ 4-CH₃—C₆H₄ L 7.54˜6.89(m, 9H), 4.49(E) 4.31(Z) (s, 2H), 3.32(s, 3H), 367(28), 148(100), 120(68), 2.34(s, 3H)) 92(52) 6 C₆H₅ CH₃ 4-C₂H₃—C₆H₄ L 7.57˜7.01(m, 9H), 4.48(E) 4.30(Z) (s, 2H), 3.30(s, 3H), 381(68), 148(100), 120(75), 2.64(q, 2H), 1.21(t, 3H) 91(74), 77(76) 7 C₆H₅ CH₃ 3,4-(CH₃)₂—C₆H₃ L 7.51˜7.02(m, 8H), 4.49(E) 4.31(Z) (s, 2H), 3.31(s, 3H), 381(25), 148(92), 120(100), 2.30(s, 6H) 91(46), 77(59) 8 C₆H₅ CH₃ 3,5-(CH₃)₂—C₆H₃ L 7.58˜6.85(m, 8H), 4.48(E) 4.29(Z) (s, 2H), 3.32(s, 3H), 381(25), 148(100), 120(59), 2.31(s, 6H) 92(28) 9 C₆H₅ CH₃ 3-CH₃O—C₆H₄ L 7.65˜6.79(m, 9H), 4.49(E) 4.30(Z) (s, 2H), 3.85(s, 3H), 383(46), 364(28), 148(100), 3.33(s, 3H) 120(99) 10 C₆H₅ CH₃ 4-CH₃O—C₆H₄ L 7.66˜6.81(m, 9H), 4.49(E) 4.31(Z) (s, 2H), 3.86(s, 3H), 383(51), 207(55), 148(100), 3.32(s, 3H) 120(59) 11 C₆H₅ CH₃ 4-C₂H₃O—C₆H₄ L 7.42˜6.80(m, 9H), 4.48(E) 4,30(Z) (s, 2H), 3.98(q, 2H), 397(49), 249(30), 148(100), 3.32(s, 3H), 1.39(t, 3H) 120(81) 12 C₆H₅ CH₃ 3,4-OCH₂O—C₆H₃ L 7.68˜6.82(m, 8H), 5.92(s, 2H), 4.49(E) 4.30(Z) (s, 2H), 397(35), 148(100), 120(70), 3.33(s, 3H) 77(43) 13 C₆H₅ CH₃ 3-CF₃—C₆H₄ L 7.68˜6.91(m, 9H), 4.48(E) 4.31(Z) (s, 2H), 3.31(s, 3H) 421(35), 402(19), 148(100), 120(99), 91(54) 14 C₆H₅ CH₃ 3-F—C₆H₄ L 7.62˜6.99(m, 9H), 4.49(E) 4.31(Z) (s, 2H), 3.32(s, 3H) 371(40), 148(100), 120(91), 96(41), 77(37) 15 C₆H₅ CH₃ 4-F—C₆H₄ L 7.68˜6.98(m, 9H), 4.48(E) 4.30(Z) (s, 2H), 3.33(s, 3H) 371(30), 148(100), 120(78), 77(42) 16 C₆H₅ CH₃ 3-Cl—C₆H₄ L 7.72˜7.01(m, 9H), 4.49(E) 4.30(Z) (s, 2H), 3.34(s, 3H) 387(62), 148(100), 120(45), 77(47) 17 C₆H₅ CH₃ 4-Cl—C₆H₄ L 7.65˜6.98(m, 9H), 4.48(E) 4.31(Z) (s, 2H), 3.35(s, 3H) 387(59), 148(100), 120(95), 91(46) 18 C₆H₅ CH₃ 3,5-Cl₂—C₆H₃ L 7.52˜7.09(m, 8H), 4.49(E) 4.32(Z) (s, 2H), 3.31(s, 3H) 421(25), 148(100), 120(84), 77(48) 19 C₆H₅ CH₃ C₄H₃S-2-yl L 7.62˜6.95(m, 8H), 4.49(E) 4.32(Z) (s, 2H), 3.32(s, 3H) 359(10), 148(100), 120(58), 77(15) 20 4-CH₃O—C₆H₄ CH₃ C₆H₅ L 7.52˜6.87(m, 9H), 4.49(E) 4.31(Z) (s, 2H), 3.85(s, 3H), 383(12), 178(100), 144(81), 3.32(s, 3H) 121(48) 21 4-CH₃O—C₆H₄ CH₃ 3-CH₃—C₆H₄ L 7.43˜6.76(m, 8H), 4.48(E) 4.29(Z) (s, 2H), 3.85(s, 3H), 397(47), 178(100), 147(40) 3.31(s, 3H), 2.35(s, 3H) 22 4-CH₃O—C₆H₄ CH₃ 4-CH₃—C₆H₄ L 7.49˜6.79(m, 8H), 4.48(E) 4.28(Z) (s, 2H), 3.84(s, 3H), 397(100), 372(33), 178(98), 3.31(s, 3H), 2.35(s, 3H) 150(53) 23 4-CH₃O—C₆H₄ CH₃ 3,4-(CH₃)₂—C₆H₃ 81˜82 7.55˜6.79(m, 7H), 4.49(E) 4.29(Z) (s, 2H), 3.85(s, 3H), 411(40), 178(100), 147(69) 3.33(s, 3H), 2.31(s, 6H) 24 4-CH₃O—C₆H₄ CH₃ 3,5-(CH₃)₂—C₆H₃ L 7.62˜6.78(m, 7H), 4.49(E) 4.30(Z) (s, 2H), 3.86(s, 3H), 411(51), 178(100), 147(47), 3.32(s, 3H), 2.30(s, 6H) 121(36) 25 4-CH₃O—C₆H₄ CH₃ 3-CH₃—C₆H₄ L 7.56˜6.72(m, 8H), 4.49(E) 4.32(Z) (s, 2H), 3.87(s, 3H), 413(24), 178(100), 147(37) 3.85(s, 3H), 2.30(s, 3H) 26 4-CH₃O—C₆H₄ CH₃ 3,4-OCH₂O—C₆H₃ L 7.59˜6.52(m, 7H), 5.94(s, 2H), 4.49(E) 4.31(Z) (s, 2H), 427(41), 178(100), 147(25), 3.86(s, 3H), 3.31(s, 3H) 121(24) 27 4-CH₃O—C₆H₄ CH₃ 3,5-Cl—C₆H₄ L 7.56˜6.85(m, 8H), 4.49(E) 4.30(Z) (s, 2H), 3.86(s, 3H), 417(18), 178(100), 147(46), 3.34(s, 3H) 121(41) 28 4-CH₃O—C₆H₄ CH₃ 4-Cl—C₆H₄ 82˜83 7.49˜6.87(m, 8H), 4.48(E) 4.30(Z) (s, 2H), 3.85(s, 3H), 417(20), 178(100), 147(88), 3.42(s, 3H) 121(58) 29 4-CH₃O—C₆H₄ CH₃ 3,5-Cl—C₆H₄ L 7.71˜6.98(m, 7H), 4.49(E) 4.31(Z) (s, 2H), 3.85(s, 3H), 451(35), 178(100), 147(82), 3.32(s, 3H) 121(70) 30 4-F—C₆H₄ CH₃ C₆H₅ L 7.54˜7.03(m, 9H), 4.49(E) 4.31(Z) (s, 2H), 3.53(s, 3H), 371(41), 166(100), 138(84), 109(78) 31 4-F—C₆H₄ CH₃ 3-CH₃—C₆H₄ L 7.32˜7.02(m, 8H), 4.49(E) 4.30(Z) (s, 2H), 3.30(s, 3H), 385(43), 166(100), 138(82), 2.35(s, 3H) 109(79), 95(30) 32 4-F—C₆H₄ CH₃ 4-CH₃—C₆H₄ L 7.36˜7.00(m, 8H), 4.49(E) 4.31(Z) (s, 2H), 3.32(s, 3H), 385(21), 166(100), 138(94), 2.33(s, 3H) 109(80) 33 4-F—C₆H₄ CH₃ 3,5-(CH₃)₂—C₆H₃ L 7.30˜6.93(m, 7H), 4.49(E) 4.30(Z) (s, 2H), 3.31(s, 3H), 399(50), 166(100), 138(76), 2.32(s, 6H) 109(69) 34 4-F—C₆H₄ CH₃ 3-CH₃O—C₆H₄ L 7.31˜6.83(m, 8H), 4.48(E) 4.30(Z) (s, 2H), 3.86(s, 3H), 401(57), 166(100), 138(67), 3.32(s, 3H) 109(45) 35 4-F—C₆H₄ CH₃ 4-CH₃O—C₆H₄ L 7.35˜6.78(m, 8H), 4.49(E) 4.30(Z) (s, 2H), 3.84(s, 3H), 401(42), 166(100), 138(52), 3.33(s, 3H) 109(44) 36 4-F—C₆H₄ CH₃ 3-F—C₆H₄ L 7.39˜6.94(m, 8H), 4.48(E) 4.31(Z) (s, 2H), 3.31(s, 3H) 389(41), 166(89), 138(100), 109(80), 95(30) 37 4-F—C₆H₄ CH₃ 4-F—C₆H₄ L 7.46˜6.94(m, 8H), 4.49(E) 4.31(Z) (s, 2H), 3.32(s, 3H) 389(56), 166(100), 138(91), 109(76), 95(29) 38 4-F—C₆H₄ CH₃ 3-Cl—C₆H₄ L 7.48˜7.06(m, 8H), 4.49(E) 4.32(Z) (s, 2H), 3.33(s, 3H) 405(26), 166(60), 138(42), 109(39), 43(100) 39 4-F—C₆H₄ CH₃ 4-Cl—C₆H₄ L 7.45˜7.05(m, 8H), 4.48(E) 4.30(Z) (s, 2H), 3.32(s, 3H) 405(41), 166(100), 138(84), 109(73), 95(35) 40 4-F—C₆H₄ CH₃ 3.5-Cl₂—C₆H₃ L 7.34˜7.08(m, 7H), 4.49(E) 4.31(Z) (s, 2H), 3.30(s, 3H) 439(46), 166(100), 138(89), 109(90), 95(38) 41 4-Cl—C₆H₄ CH₃ 3,5-Cl₂—C₆H₃ 136˜137 7.50˜7.05(m, 7H), 4.48(E) 4.30(Z) (s, 2H), 3.31(s, 3H) 455(31), 182(56), 147(100), 118(35), 77(24) 42 2,4-F₂—C₆H₃ CH₃ 3-Cl—C₆H₄ L 7.45˜6.85(m, 7H), 4.49(E) 4.31(Z) (s, 2H), 3.32(s, 3H) 423(21), 184(34), 156(24), 127(100) 43 2,4-Cl₂—C₆H₃ CH₃ 4-F—C₆H₄ L 7.79˜6.87(m, 7H), 4.48(E) 4.31(Z) (s, 2H), 3.33(s, 3H) 439(34), 216(57), 181(100), 145(50) 44 C₆H₅ C₂H₅ C₆H₅ L 7.65˜7.09(m, 10H), 4.41(E) 4.28(Z) (s, 2H), 3.75(q, 2H), 367(12), 162(100), 134(79), 1.13(t, 3H) 106(57), 91(55) 45 C₆H₅ C₂H₅ 3-CH₃—C₆H₄ L 7.49˜7.01(m, 9H), 4.42(E) 4.29(Z) (s, 2H), 3.76(q, 2H), 381(100), 363(10), 162(56), 2.39(s, 3H), 1.14(t, 3H) 134(64) 46 C₆H₅ C₂H₅ 3-CH₃O—C₆H₄ L 7.62˜6.81(m, 9H), 4.43(E) 4.28(Z) (s, 2H), 3.85(s, 3H), 397(29), 378(16), 162(99), 3.74(q, 2H), 1.14(t, 3H) 134(100), 106(78) 47 C₆H₅ C₂H₅ 4-C₂H₃O—C₆H₄ L 7.42˜6.75(m, 9H), 4.42(E) 4.28(Z) (s, 2H), 3.94(q, 2H), 411(25), 221(54), 162(100), 3.72(q, 2H), 1.34(t, 3H), 1.13(t, 3H) 134(72) 48 C₆H₅ C₂H₅ 3-CF₃—C₆H₄ L 7.82˜7.02(m, 9H), 4.42(E) 4.29(Z) (s, 2H), 3.74(q, 2H), 435(16), 162(100), 134(89), 1.14(t, 3H) 106(46) 49 C₆H₅ C₂H₅ 3-F—C₆H₄ L 7.49˜6.90(m, 9H), 4.42(E) 4.28(Z) (s, 2H), 3.75(q, 2H), 385(30), 162(100), 134(71), 1.13(t, 3H) 106(43) 50 C₆H₅ C₂H₅ 4-F—C₆H₄ L 7.62˜6.92(m, 9H), 4.41(E) 4.29(Z) (s, 2H), 3.76(q, 2H), 385(39), 162(100), 133(80), 1.14(t, 3H) 91(53) 51 C₆H₃ C₂H₅ 4-Cl—C₆H₄ L 7.57˜6.98(m, 9H), 4.42(E) 4.29(Z) (s, 2H), 3.76(q, 2H), 401(40), 162(100), 134(56) 1.14(t, 3H) 52 C₆H₃ C₂H₅ C₄H₃S-2-yl L 7.68˜6.93(m, 8H), 4.42(E) 4.28(Z) (s, 2H), 3.75(q, 2H), 373(31), 162(100), 134(32) 1.16(t, 3H) 53 4-CH₃—C₆H₄ C₂H₅ C₆H₃ L 7.49˜6.94(m, 9H), 4.43(E) 4.29(Z) (s, 2H), 3.74(q, 2H), 381(55), 176(100, 105(44) 2.39(s, 3H), 1.13(t, 3H) 54 4-CH₃—C₆H₄ C₂H₅ 4-F—C₆H₄ L 7.63˜6.89(m, 8H), 4.42(E) 4.29(Z) (s, 2H), 3.74(q, 2H), 399(55), 176(100), 148(55) 2.38(s, 3H), 1.12(t, 3H) 55 4-CH₃O—C₆H₄ C₂H₅ C₆H₃ L 7.49˜6.85(m, 9H), 4.41(E) 4.27(Z) (s, 2H), 3.81(s, 3H), 397(23), 378(12), 193(100), 3.72(q, 2H), 1.13(t, 3H) 165(36) 56 4-CH₃O—C₆H₄ C₂H₅ 4-F—C₆H₄ L 7.48˜6.84(m, 8H), 4.42(E) 4.28(Z) (s, 2H), 3.82(s, 3H), 415(14), 192(100), 164(43), 3.75(q, 2H), 1.12(t, 3H) 121(75) 57 3-CF₃—C₆H₄ C₂H₅ C₆H₃ 52˜53 7.81˜7.23(m, 9H), 4.43(E) 4.29(Z) (s, 2H), 3.75(q, 2H), 435(26), 221(100), 174(61), 1.13(t, 3H) 159(69) 58 3-CF₃—C₆H₄ C₂H₅ 4-CH₃—C₆H₄ 48˜49 7.86˜7.02(m, 8H), 4.41(E) 4.28(Z) (s, 2H), 3.72(q, 2H), 449(10), 230(100), 202(36), 2.38(s, 3H), 1.12(t, 3H) 174(27) 59 3-CF₃—C₆H₄ C₂H₅ 4-F—C₆H₄ L 7.89˜6.85(m, 8H), 4.41(E) 4.29(Z) (s, 2H), 3.73(q, 2H), 453(26), 231(100), 201(63) 1.14(t, 3H) 60 2-Cl—C₆H₄ C₂H₃ C₆H₃ L 7.60˜7.12(m, 9H), 4.40(E) 4.28(Z) (s, 2H), 4.02(m, 1H), 401(72), 382(15), 196(100), 3.48(m, 1H), 1.12(t, 3H) 168(44), 146(35) 61 2-Cl—C₆H₄ C₂H₅ 4-CH₃—C₆H₄ L 7.62˜7.02(m, 8H), 4.40(E) 4.28(Z) (s, 2H), 4.06(m, 1H), 415(26), 196(100), 118(35) 3.49(m, 1H), 2.39(s, 3H), 1.14(t, 3H) 62 3-Cl—C₆H₄ C₂H₅ C₆H₃ L 7.49˜6.94(m, 9H), 4.41(E) 4.28(Z) (s, 2H), 3.73(q, 2H), 401(14), 196(100), 168(24), 1.13(t, 3H) 146(27) 63 4-Cl—C₆H₄ C₂H₅ C₆H₅ L 7.50˜6.90(m, 9H), 4.40(E) 4.28(Z) (s, 2H), 3.74(q, 2H), 401(10), 196(100), 146(37), 1.14(t, 3H) 118(18) 64 4-Cl—C₆H₄ C₂H₅ 4-CH₃—C₆H₄ 70˜71 7.62˜6.95(m, 8H), 4.40(E) 4.29(Z) (s, 2H), 3.76(q, 2H), 415(12), 196(81), 161(100), 2.39(s, 3H), 1.14(t, 3H) 118(27) 65 C₆H₅ n-C₃H₇ C₆H₃ L 7.50˜7.02(m, 10H), 4.40(E) 4.25(Z) (s, 2H), 3.65(t, 2H), 381(11), 176(100), 134(84), 1.68˜1.41(m, 2H), 0.91(t, 3H) 106(93), 77(62) 66 C₆H₅ n-C₃H₇ 4-CH₃—C₆H₄ L 7.62˜6.97(m, 9H), 4.40(E) 4.26(Z) (s, 2H), 3.64(t, 2H), 395(20), 377(13), 176(100), 2.32(s, 3H), 1.67˜1.42(m, 2H), 0.91(t, 3H) 67 4-CH₃O—C₆H₄ n-C₃H₇ C₆H₃ L 7.53˜6.86(m, 9H), 4.40(E) 4.25(Z) (s, 2H), 3.81(s, 3H), 411(24), 206(100), 178(35), 3.65(t, 2H), 1.65˜1.41(m, 2H), 0.91(t, 3H) 164(48), 136(42) 68 4-CH₃O—C₆H₄ n-C₃H₇ 4-CH₃—C₆H₄ L 7.62˜6.79(m, 8H), 4.39(E) 4.25(Z) (s, 2H), 3.83(s, 3H), 425(29), 406(14), 203(100) 3.65(t, 2H), 2.32(s, 3H), 1.68˜1.42(m, 2H), 0.92(t, 3H) 69 C₆H₃ i-C₃H₇ C₆H₃ 54˜55 7.50˜7.01(m, 10H), 5.09˜4.87(m, 1H), 4.30(E) 4.14(Z) 381(12), 176(59), 134(100), (s, 2H), 1.08(d, 6H) 106(97), 77(89) 70 C₆H₃ i-C₃H₇ 3-CH₃—C₆H₄ L 7.62˜6.82(m, 9H), 5.10˜4.89(m, 1H), 4.29(E) 4.16(Z) 395(39), 176(34), 134(100), (s, 2H), 2.39(s, 3H), 1.09(d, 6H) 106(69) 71 C₆H₃ i-C₃H₇ 4-CH₃—C₆H₄ 67˜68 7.62˜6.97(m, 9H), 5.28˜4.86(m, 1H), 4.29(E) 4.15(Z) 395(65), 376(49), 176(100), (s, 2H), 2.46(s, 3H), 1.09(d, 6H) 106(76) 72 C₆H₃ i-C₃H₇ 3,5-(CH₃)₂—C₆H₃ L 7.64˜6.85(m, 8H), 5.28˜4.88(m, 1H), 4.30(E) 4.16(Z) 409(56), 134(100), 106(87), (s, 2H), 2.38(s, 6H), 1.09(d, 6H) 77(52) 73 C₆H₃ i-C₃H₇ 3-CH₃O—C₆H₄ L 7.51˜6.79(m, 9H), 5.19˜4.84(m, 1H), 4.28(E) 4.14(Z) 411(30), 176(39), 134(100), (s, 2H), 3.80(s, 3H), 1.08(d, 6H) 106(50) 74 C₆H₃ i-C₃H₇ 4-CH₃O—C₆H₃ 48˜49 7.71˜6.95(m, 9H), 5.21˜4.85(m, 1H), 4.29(E) 4.15(Z) 411(33), 176(57), 134(100), (s, 2H), 3.81(s, 3H), 1.09(d, 6H) 106(74) 75 C₆H₃ i-C₃H₇ 4-C₂H₃O—C₆H₄ L 7.48˜6.79(m, 9H), 5.10˜4.84(m, 1H), 4.28(E) 4.16(Z) 425(70), 176(63), 134(100), (s, 2H), 4.40(q, 2H), 1.38(t, 3H), 1.09(d, 6H) 106(69), 84(55) 76 C₆H₃ i-C₃H₇ 3,4-OCH₂O—C₆H₃ L 7.59˜6.75(m, 8H), 5.96(s, 2H), 5.11˜4.86(m, 1H), 425(15), 219(30), 134(100), 4.29(E) 4.16(Z) (s, 2H), 1.08(d, 6H) 106(60) 77 C₆H₃ i-C₃H₇ 3-F—C₆H₄ L 7.50˜6.91(m, 9H), 5.10˜4.82(m, 1H), 4.29(E) 4.14(Z) 399(40), 134(100), 106(70) (s, 2H), 1.09(d, 6H) 78 C₆H₃ i-C₃H₇ 4-F—C₆H₄ L 7.54˜6.89(m, 9H), 5.09˜4.84(m, 1H), 4.28(E) 4.15(Z) 399(35), 176(45), 134(100), (s, 2H), 1.08(d, 6H) 106(83) 79 C₆H₃ i-C₃H₇ 3-Cl—C₆H₄ L 7.69˜6.94(m, 9H), 5.11˜4.88(m, 1H), 4.29(E) 4.15(Z) 415(45), 176(31), 134(100), (s, 2H), 1.08(d, 6H) 106(65) 80 C₆H₃ i-C₃H₇ 4-Cl—C₆H₄ 72˜73 7.87˜6.87(m, 9H), 5.21˜4.87(m, 1H), 4.28(E) 4.14(Z) 415(25), 176(28), 134(100), (s, 2H), 1.09(d, 6H) 106(73), 78(34) 81 C₆H₃ i-C₃H₇ C₄H₃S-2-yl 63˜64 7.50˜6.94(m, 8H), 5.18˜4.81(m, 1H), 4.29(E) 4.16(Z) 387(22), 176(31), 134(100), (s, 2H), 1.08(d, 6H) 106(85), 77(41), 43(46) 82 2-CH₃—C₆H₄ i-C₃H₇ C₆H₃ L 7.61˜6.97(m, 9H), 5.00˜4.78(m, 1H), 4.28(E) 4.17(Z) 395(46), 148(100), 120(47), (dd, 2H), 2.32(s, 3H), 1.27(d, 3H), 1.02(d, 3H) 45(23) 83 2-CH₃—C₆H₄ i-C₃H₇ 4-CH₃—C₆H₄ L 7.48˜6.95(m, 8H), 4.95˜4.75(m, 1H), 4.29(E) 4.15(Z) 409(9), 190(34), 148(100), (dd, 2H), 2.33(s, 3H), 2.31(s, 3H), 1.30(d, 3H), 120(80), 118(30), 91(30), 1.00(d, 3H) 45(42) 84 2-CH₃—C₆H₄ i-C₃H₇ 3,4-(CH₃)₂—C₆H₃ L 7.42˜7.00(m, 7H), 4.96˜4.76(m, 1H), 4.28(E) 4.15(Z) 423(15), 148(100), 120(49), (dd, 2H), 2.33(s, 3H), 2.30(s, 6H), 1.30(d, 3H), 45(22) 1.02(d, 3H) 85 2-CH₃—C₆H₄ i-C₃H₇ 3,5-(CH₃)₂—C₆H₃ L 7.40˜6.85(m, 7H), 4.95˜4.76(m, 1H), 4.28(E) 4.16(Z) 423(20), 148(100), 120(45), (dd, 2H), 2.33(s, 3H), 2.31(s, 6H), 1.31(d, 3H), 45(24) 1.01(d, 3H) 86 2-CH₃—C₆H₄ i-C₃H₇ 3-CH₃O—C₆H₄ L 7.46˜6.75(m. 8H), 4.90˜4.72(m, 1H), 4.28(E) 4.16(Z) 425(R), 148(100), 120(82), (dd, 2H), 3.82(s, 3H), 2.32(s, 3H), 1.28(d, 3H), 45(39) 0.98(d, 3H) 87 2-CH₃—C₆H₄ i-C₃H₇ 4-CH₃O—C₆H₄ L 7.40˜6.80(m, 8H), 4.91˜4.75(m, 1H), 4.28(E) 4.15(Z) 425(8), 148(100), 120(63), (dd, 2H), 3.81(s, 3H), 2.31(s, 3H), 1.29(d, 3H), 45(25) 0.99(d, 3H) 88 2-CH₃—C₆H₄ i-C₃H₇ 3-F—C₆H₄ L 7.38˜6.87(m, 8H), 4.91˜4.72(m, 1H), 4.28(E) 4.16(Z) 413(54), 148(100), 120(68), (dd, 2H), 2.31(s, 3H), 1.29(d, 3H), 0.98(d, 3H) 45(39) 89 2-CH₃—-C₆H₄ i-C₃H₇ 4-F—C₆H₄ L 7.51˜6.95(m, 8H), 4.97˜4.78(m, 1H), 4.28(E) 4.15(Z) 413(22), 190(89), 148(100), (dd, 2H), 2.30(s, 3H), 1.25(d, 3H), 1.01(d, 3H) 120(94), 91(73) 90 2-CH₃—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.54˜7.00(m, 8H), 4.96˜4.74(m, 1H), 4.27(E) 4.16(Z) 429(16), 148(100), 120(51), (dd, 2H), 2.28(s, 3H), 1.30(d, 3H), 1.01(d, 3H) 45(23) 91 2-CH₃—C₆H₄ i-C₃H₇ 4-Cl—C₆H₄ L 7.50˜7.00(m, 8H), 4.95˜4.76(m, 1H), 4.28(E) 4.15(Z) 429(30), 148(100), 120(52), (dd, 2H), 2.29(s, 3H), 1.28(d, 3H), 1.00(d, 3H) 84(32), 45(36) 92 2-CH₃—C₆H₄ i-C₃H₇ 3,5-Cl₂—C₆H₃ L 7.52˜7.00(m, 7H), 4.95˜4.75(m, 1H), 4.27(E) 4.15(Z) 463(16), 148(100), 120(73), (dd, 2H), 228(s, 3H), 1.30(d, 3H), 1.01(d, 3H) 45(45) 93 3-CH₃—C₆H₄ i-C₃H₇ C₆H₅ 64˜65 7.45˜6.80(m, 9H), 5.02˜4.79(m, 1H), 4.30(E) 4.12(Z) 395(14), 190(56), 148(100), (s, 2H), 2.35(s, 3H), 1.08(d, 6H) 120(95), 91(35) 94 3-CH₃—C₆H₄ i-C₃H₇ 3-CH₃—C₆H₄ L 7.32˜6.79(m, 8H), 5.03˜4.80(m, 1H), 4.30(E) 4.15(Z) 409(11), 190(28), 148(100), (s, 2H), 2.34(s, 3H), 2.30(s, 3H), 1.09(d, 6H) 120(51), 84(39) 95 3-CH₃—C₆H₄ i-C₃H₇ 4-C₂H₅—C₆H₄ 76˜77 7.32˜6.80(m, 8H), 5.04˜4.83(m, 1H), 4.28(E) 4.14(Z) 409(36), 190(60), 148(100), (s, 2H), 2.38(s, 3H), 2.31(s, 3H), 1.05(d, 6H) 120(54) 96 3-CH₃—C₆H₄ i-C₃H₇ 4-C₂H₅—C₆H₄ 66˜67 7.40˜6.81(m, 8H), 5.04˜4.84(m, 1H), 4.30(E) 4.16(Z) 423(41), 190(47), 148(100), (s, 2H), 2.65(q, 2H), 2.38(s, 3H), 1.26(1, 3H), 120(60), 91(21) 1.09(d, 6H) 97 3-CH₃—C₆H₄ i-C₃H₇ 3,4-(CH₃)₂—C₆H₃ L 7.48˜6.81(m, 7H), 5.03˜4.85(m, 1H), 4.31(E) 4.17(Z) 423(56), 190(39), 148(100), (s, 2H), 2.39(s, 3H), 2.25(s, 6H), 1.08(d, 6H) 120(52), 91(20) 98 3-CH₃—C₆H₄ i-C₃H₇ 3,5-(CH₃)₂—C₆H₃ 60˜61 7.38˜6.80(m, 7H), 5.05˜4.85(m, 1H), 4.29(E) 4.15(Z) 423(57), 190(69), 148(100), (s, 2H), 2.35(s, 3H), 2.29(s, 6H), 1.07(d, 6H) 120(63), 91(24) 99 3-CH₃—C₆H₄ i-C₃H₇ 3-CH₃—C₆H₄ 46˜47 7.41˜6.82(m, 8H), 5.06˜4.86(m, 1H), 4.30(E) 4.16(Z) 425(58), 190(37), 148(100), (s, 2H), 3.80(s, 3H), 2.35(s, 3H), 1.10(d, 6H) 120(53) 100 3-CH₃—C₆H₄ i-C₃H₇ 4-CH₃O—C₆H₄ 68˜69 7.37˜6.79(m, 8H), 5.01˜4.80(m, 1H), 4.30(E) 4.15(Z) 425(31), 190(11), 148(100), (s, 2H), 3.82(s, 3H), 2.34(s, 3H), 1.07(d, 6H) 1.20(79), 91(30) 101 3-CH₃—C₆H₄ i-C₃H₇ 3-F—C₆H₄ 42˜43 7.35˜6.81(m, 8H), 5.01˜4.78(m, 1H), 4.30(E) 4.14(Z) 413(57), 190(37), 148(100), (s, 2H) 2.35(s, 3H), 1.09(d, 6H) 120(54) 102 3-CH₃—C₆H₄ i-C₃H₇ 4-F—C₆H₄ L 7.50˜6.85(m, 8H), 5.04˜4.85(m, 1H), 4.30(E) 4.16(Z) 413(51), 148(100), 120(90) (s, 2H), 2.39(s, 3H), 1.09(d, 6H) 103 3-CH₃—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.48˜6.78(m, 8H), 5.04˜4.85(m, 1H), 4.31(E) 4.14(Z) 429(25), 148(100), 120(83) (s, 2H), 2.38(s, 3H), 1.08(d, 6H) 104 3-CH₃—C₆H₄ i-C₃H₇ 4-Cl—C₆H₄ 56˜57 7.40˜6.62(m, 8H), 5.02˜4.85(m, 1H), 4.30(E) 4.15(Z) 429(55), 190(23), 148(100), (s, 2H), 2.38(s, 3H), 1.08(d, 6H) 120(53) 105 3-CH₃—C₆H₄ i-C₃H₇ 3,5-Cl₂—C₆H₃ 58˜59 7.35˜6.80(m, 7H), 5.00˜4.80(m, 1H), 4.31(E) 4.17(Z) 463(51), 148(100), 120(37) (s, 2H), 2.35(s, 3H), 1.07(d, 6H) 106 3-CH₃O—C₆H₄ i-C₃H₇ C₆H₅ 80˜81 7.50˜6.58(m, 9H), 5.08˜4.85(m, 1H), 4.29(E) 4.14(Z) 411(28), 208(100), 165(82), (s, 2H), 3.82(s, 3H), 1.09(d, 6H) 137(36) 107 3-CH₃O—C₆H₄ i-C₃H₇ 4-CH₃—C₆H₄ 93˜94 7.52˜6.53(m, 8H), 5.23˜4.78(m, 1H), 4.30(E) 4.15(Z) 425(33), 375(100), 118(78) (s, 2H), 3.82(s, 3H), 2.41(s, 3H), 1.12(d, 6H) 108 3-CH₃O—C₆H₄ i-C₃H₇ 4-F—C₆H₄ 50˜51 7.45˜6.55(m, 8H), 5.02˜4.85(m, 1H), 4.31(E) 4.16(Z) 429(52), 206(82), 164(100), (s, 2H), 3.80(s, 3H), 1.09(d, 6H) 136(86), 45(24) 109 3,4-CH₃O—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.51˜6.76(m, 8H), 5.02˜4.82(m, 1H), 4.30(E) 4.14(Z) 445(50), 206(50), 164(100), (s, 2H), 3.82(s, 3H), 1.02(d, 6H) 136(68), 45(54) 110 3-CH₃O—C₆H₄ i-C₃H₇ 4-Cl—C₆H₄ 60˜61 7.45˜6.58(m, 8H), 5.02˜4.85(m, 1H), 4.29(E) 4.14(Z) 445(24), 206(66), 164(100), (s, 2H), 3.81(s, 3H), 1.10(d, 6H) 136(92), 45(37) 111 3-CH₃O—C₆H₄ i-C₃H₇ 3,5-Cl₂—C₆H₃ L 7.41˜6.61(m, 7H), 5.00˜4.84(m, 1H), 4.30(E) 4.15(Z) 479(51), 206(54), 164(100), (s, 2H), 3.81(s, 3H), 1.09(d, 6H) 137(74), 45(26) 112 4-CH₃O—C₆H₄ i-C₃H₇ C₆H₃ L 7.49˜6.81(m, 9H), 5.04˜4.82(m, 1H), 4.29(E) 4.13(Z) 411(56), 206(68), 164(100), (s, 2H), 3.81(s, 3H), 1.04(d, 6H) 136(52), 121(74) 113 4-CH₃O—C₆H₄ i-C₃H₇ 3-CH₃—C₆H₄ L 7.55˜6.88(m, 8H), 5.12˜4.79(m, 1H), 4.31(E) 4.16(Z) 425(26), 210(81), 168(100), (s, 2H), 3.81(s, 3H), 2.38(s, 3H), 1.08(d, 6H) 140(53), 133(49), 45(51) 114 4-CH₃O—C₆H₄ i-C₃H₇ 4-CH₃—C₆H₄ 87˜88 7.62˜6.98(m, 8H), 5.21˜4.82(m, 1H), 4.29(E) 4.14(Z) 425(14), 406(10), 203(100), (s, 2H), 3.82(s, 3H), 2.35(s, 3H), 1.08(d, 6H) 69(27) 115 4-CH₃O—C₆H₄ i-C₃H₇ 4-CH₃O—C₆H₄ L 7.40˜6.81(m, 8H), 5.02˜4.83(m, 1H), 4.29(E) 4.15(Z) 441(30), 206(76), 164(100), (s, 2H), 3.81(s, 3H), 3.79(s, 3H), 1.08(d, 6H) 136(42), 121(47) 116 4-CH₃O—C₆H₄ i-C₃H₄ 4-F—C₆H₄ L 7.49˜6.86(m, 8H), 5.03˜4.84(m, 1H), 4.30(E) 4.15(Z) 429(57), 206(36), 164(100), (s, 2H), 3.82(s, 3H), 1.10(d, 6H) 136(52) 117 4-CH₃O—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.49˜6.88(m, 8H), 5.03˜4.85(m, 1H), 4.29(E) 4.17(Z) 445(62), 164(100), 121(42) (s, 2H), 3.82(s, 3H), 1.10(d, 6H) 118 3-CF₃—C₆H₄ i-C₃H₇ C₆H₃ L 7.80˜7.23(m, 9H), 5.12˜4.89(m, 1H), 4.30(E) 4.15(Z) 449(36), 430(19), 244(100), (s, 2H), 1.02(d, 6H) 174(40) 119 3-CF₂—C₆H₄ i-C₃H₇ 3,4-OCH₂O—C₆H₃ L 7.95˜6.72(m, 7H), 5.95(s, 2H), 5.28˜4.84(m, 1H), 493(35), 244(21), 202(100) 4.29(E) 4.14(Z) (s, 2H), 1.09(d, 6H) 120 3-CF₃—C₆H₄ i-C₃H₇ 4-F—C₆H₄ L 7.81˜6.98(m, 8H), 5.05˜4.92(m, 1H), 4.29(E) 4.16(Z) 467(30), 244(35), 203(100), (s, 2H), 1.12(d, 6H) 174(78), 145(65) 121 3-CF₄—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.79˜7.18(m, 8H), 5.09˜4.89(m, 1H), 4.30(E) 4.14(Z) 483(24), 202(100), 174(31) (s, 2H), 1.10(d, 6H) 122 4-F—C₆H₄ i-C₃H₇ C₆H₅ 75˜76 7.51˜6.91(m, 9H), 5.15˜4.67(m, 1H), 4.29(E) 4.14(Z) 399(70), 380(26), 194(100), (s, 2H), 1.02(d, 6H) 152(94), 123(91), 109(36) 123 4-F—C₆H₄ i-C₃H₇ 4-CH₃—C₆H₄ 68˜69 7.46˜6.98(m, 8H), 5.21˜4.78(m, 1H), 4.30(E) 4.15(Z) 413(45), 394(100), 109(36) (s, 2H), 2.46(s, 3H), 1.07(d, 6H) 124 4-F—C₆H₄ i-C₃H₇ 3-CH₃O—C₆H₄ L 7.51˜6.91(m, 8H), 5.51˜4.67(m, 1H), 4.29(E) 4.17(Z) 429(22), 410(15), 194(47), (s, 2H), 3.85(s, 3H), 1.02(d, 6H) 152(100), 124(41) 125 4-F—C₆H₄ i-C₃H₇ 3-CF₃—C₆H₄ L 7.79˜7.05(m, 1H), 5.23˜4.82(m, 1H), 4.30(E) 4.14(Z) 467(15), 194(51), 152(100), (s, 2H), 1.08(d, 6H) 124(36) 126 4-F—C₆H₄ i-C₃H₇ 4-F—C₆H₄ L 7.49˜6.98(m, 8H), 5.06˜4.87(m, 1H), 4.29(E) 4.16(Z) 417(36), 194(92), 152(100), (m, 2H), 1.11(d, 6H) 122(86) 127 4-F—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.41˜7.01(m, 8H), 5.02˜4.85(m, 1H), 4.30(E) 4.14(Z) 433(45), 152(100), 124(41) (m, 2H), 1.02(d, 6H) 128 4-F—C₆H₄ i-C₃H₇ C₄H₃S-2-yl L 7.46˜6.97(m, 7H), 5.21˜4.75(m, 1H), 4.29(E) 4.15(Z) 405(31), 194(36), 152(100) (s, 2H), 1.09(d, 6H) 122(21), 109(24) 129 2-Cl—C₆H₄ i-C₃H₇ C₆H₃ L 7.58˜7.02(m, 9H), 4.98˜4.79(m, 1H), 4.29(E) 4.15(Z) 415(25), 168(100), 140(64), (dd, 2H, 1.24(d, 3H), 1.02(d, 3H) 45(57) 130 2-Cl—C₆H₄ i-C₃H₇ 3-CH₃—C₆H₄ L 7.61˜7.02(m, 8H), 5.03˜4.79(m, 1H), 4.31(E) 4.14(Z) 429(60), 168(100), 140(53), (dd, 2H), 2.35(s, 3H), 1.24(d, 3H), 1.02(d, 3H) 131 2-Cl—C₆H₄ i-C₃H₇ 4-CH₃—C₆H₄ L 7.61˜7.08(m, 8H), 4.98˜4.79(m, 1H), 4.30(E) 4.15(Z) 429(15), 168(100), 140(44) (dd, 2H), 2.35(s, 3H), 1.25(d, 3H), 1.02(d, 3H) 132 2-Cl—C₆H₄ i-C₃H₇ 4-C₂H₅—C₆H₄ L 7.60˜7.08(m, 8H), 4.98˜4.78(m, 1H), 4.33(E) 4.14(Z) 443(17), 210(59), 168(100), (dd, 2H), 2.65(q, 2H), 1.32(t, 3H), 1.25(d, 3H), 1.33(86), 45(78) 1.03(d, 3H) 133 2-Cl—C₆H₄ i-C₃H₇ 3,4-(CH₃)₂—C₆H₃ L 7.59˜7.02(m, 7H), 4.98˜4.79(m, 1H), 4.29(E) 4.16(Z) 443(20), 170(59), 168(100), (dd, 2H, 2.26(s, 6H), 1.23(d, 3H), 1.02(d, 3H) 140(59) 134 2-Cl—C₆H₄ i-C₃H₇ 3,5-(CH₃)₂—C₆H₃ 64˜65 7.58˜6.89(m, 7H), 5.02˜4.78(m, 1H), 4.30(E) 4.15(Z) 443(30), 168(100), 140(44) (dd, 2H), 2.28(s, 6H), 1.23(d, 3H), 1.00(d, 3H) 135 2-Cl—C₆H₄ i-C₃H₇ 3-CH₃O—C₆H₄ L 7.60˜6.80(m, 8H), 5.00˜4.80(m, 1H), 4.29(E) 4.17(Z) 445(30), 210(25), 168(100), (dd, 2H) 3.79(s, 3H), 1.27(d, 3H), 1.01(d, 3H) 140(68), 133(56), 45(36) 136 2-Cl—C₆H₄ i-C₃H₇ 4-CH₃O—C₆H₄ L 7.59˜6.87(m, 8H), 4.99˜4.78(m, 1H), 4.32(E) 4.13(Z) 445(25), 168(100), 140(49), (dd, 2H), 3.79(s, 3H), 1.25(d, 3H), 1.03(d, 3H) 45(78) 137 2-Cl—C₆H₄ i-C₃H₇ 3-F—C₆H₄ L 7.61˜6.91(m, 8H), 5.01˜4.78(m, 1H), 4.30(E) 4.18(Z) 4.33(25), 210(57), 168(100), (dd, 2H), 1.28(d, 3H), 1.02(d, 3H) 140(81), 133(56) 138 2-Cl—C₆H₄ i-C₃H₇ 4-F—C₆H₄ L 7.60˜6.98(m, 8H), 5.02˜4.79(m, 1H), 4.32(E) 4.19(Z) 433(30), 168(100), 140(67), (dd, 2H), 1.29(d, 3H), 1.03(d, 3H) 133(47) 139 2-Cl—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.59˜7.04(m, 8H), 4.99˜4.78(m, 1H), 4.33(E) 4.16(Z) 449(20), 168(100), 140(64), (dd, 2H), 1.25(d, 3H), 1.02(d, 3H) 45(75) 140 2-Cl—C₆H₄ i-C₃H₇ 4-Cl—C₆H₄ L 7.62˜7.15(m, 8H), 5.00˜4.75(m, 1H), 4.30(E) 4.17(Z) 449(15), 168(100), 140(49), (dd, 2H), 1.29(d, 3H), 1.02(d, 3H) 133(37), 45(34) 141 2-Cl—C₆H₄ i-C₃H₇ 3,5-Cl₂—C₆H₃ L 7.57˜7.01(m, 7H), 4.97˜4.79(m, 1H), 4.30(E) 4.22(Z) 483(25), 168(100), 140(77), (dd, 2H), 1.23(d, 3H), 1.02(d, 3H) 133(63) 142 3-Cl—C₆H₄ i-C₃H₇ C₆H₃ L 7.65˜6.98(m, 9H), 5.09˜4.84(m, 1H), 4.30(E) 4.15(Z) 415(10), 211(45), 169(100), (s, 2H), 1.09(d, 6H) 87(35) 143 3-Cl—C₆H₄ i-C₃H₇ 4-CH₃—C₆H₄ 79˜80 7.52˜6.53(m, 8H), 5.24˜4.72(m, 1H), 4.29(E) 4.17(Z) 429(15), 210(42), 168(100), (s, 2H), 2.34(s, 3H), 1.21(d, 6H) 140(53), 133(41) 144 3-Cl—C₆H₄ i-C₃H₇ 4-F—C₆H₄ L 7.51˜6.90(m, 8H), 5.03˜4.83(m, 1H), 4.30(E) 4.16(Z) 433(45), 210(42), 168(100), (s, 2H), 1.08(d, 6H) 140(80), 133(52) 145 3-Cl—C₆H₄ i-C₃H₇ 3-Cl—C₆H₄ L 7.69˜6.95(m, 8H), 5.09˜4.85(m, 1H), 4.31(E) 4.18(Z) 449(35), 168(100), 140(60), (s, 2H), 1.10(d, 6H) 45(8H) 146 2-Cl-4-F—C₆H₃ i-C₃H₄ C₆H₅ L 7.45˜6.92(m, 1), 5.00˜4.77(m, 1H), 4.32(E) 4.19(Z) 433(56), 193(54), 168(65), (dd, 2H), 1.29(d, 3H), 1.03(d, 3H) 151(100), 45(46) 147 2-Cl-4-F—C₆H₃ i-C₃H₇ 3-CH₃—C₆H₄ L 7.34˜6.98(m, 7H), 5.00˜4.77(m, 1H), 4.32(E) 4.17(Z) 447(35), 186(33), 84(100), (dd, 2H), 2.32(s, 3H), 1.27(d, 3H), 1.01(d, 3H) 45(49) 148 2-Cl-4-F—C₆H₃ i-C₃H₇ 4-CH₃—C₆H₄ L 7.41˜6.99(m, 7H), 5.01˜4.76(m, 1H), 4.30(E) 4.16(Z) 447(55), 193(67), 186(78), (dd, 2H), 2.33(s, 3H), 1.26(d, 3H), 1.04(d, 3H) 151(100), 45(35) 149 2-Cl-4-F—C₆H₃ i-C₃H₇ 3,4-(CH₃)₂—C₆H₃ L 7.35˜6.97(m, 6H), 5.01˜4.78(m,1H), 4.30(E) 4.19(Z) 461(56), 193(66), 186(88), (dd, 2H), 2.33(s, 6H), 1.26(d, 3H), 1.02(d, 3H) 151(100), 45(49) 150 2-Cl-4-F—C₆H₃ i-C₃H₇ 3,5-(CH₃)₂—C₆H₃ 70˜71 7.38˜6.82(m, 6H), 5.00˜4.76(m, 1H), 4.31(E) 4.16(Z) 461(31), 193(64), 186(85), (dd, 2H), 2.30(s, 6H), 1.27(d, 3H), 1.00(d, 3H) 151(100), 45(54) 151 2-Cl-4-F—C₆H₃ i-C₃H₇ 3-F—C₆H₄ L 7.40˜6.95(m, 7H), 5.00˜4.79(m, 1H), 4.31(E) 4.17(Z) 451(40), 193(61), 186(66), (dd, 2H), 1.27(d, 3H), 1.03(d, 3H) 151(100), 45(48) 152 2-Cl-4-F—C₆H₃ i-C₃H₇ 4-F—C₆H₄ L 7.47˜6.94(m, 7H), 5.00˜4.78(m, 1H), 4.32(E) 4.16(Z) 451(22), 193(52), 186(73), (dd, 2H), 1.26(d, 3H), 1.02(d, 3H) 151(100), 45(53) 153 2-Cl-4-F—C₆H₃ i-C₃H₇ 3-Cl—C₆H₄ L 7.45˜6.98(m, 7H), 5.00˜4.79(m, 1H), 4.32(E) 4.16(Z) 467(39), 193(69), 186(74), (dd, 2H), 1.28(d, 3H), 1.04(d, 3H) 151(100), 45(53) 154 2-Cl-4-F—C₆H₃ i-C₃H₇ 4-Cl—C₆H₄ L 7.44˜6.98(m, 7H), 4.98˜4.75(m, 1H), 4.30(E) 4.17(Z) 467(35), 193(71), 186(72), (dd, 2H), 1.27(d, 3H), 1.03(d, 3H) 151(100), 45(60) 155 2-Cl-4-F—C₆H₃ i-C₃H₇ 3,5-Cl₂—C₆H₃ L 7.45˜7.01(m, 6H), 5.00˜4.78(m, 1H), 4.32(E) 4.15(Z) 501(41), 193(87), 186(76), (dd, 2H), 1.27(d, 3H), 1.03(d, 3H) 151(100), 45(68) 156 3,4-Cl₂—C₆H₃ i-C₃H₇ C₆H₃ 96˜97 7.60˜6.87(m, 8H), 5.04˜4.84(m, 1H), 4.30(E) 4.15(Z) 449(30), 244,(31), 202(100), (s, 2H), 1.07(d, 6H) 167(83), 45(65) 157 3,4-Cl₂—C₆H₃ i-C₃H₇ 3-F—C₆H₄ 74˜75 7.61˜6.95(m, 7H), 5.05˜4.85(m, 1H), 4.29(E) 4.14(Z) 467(36), 244(28), 202(100), (s, 2H), 1.12(d, 6H) 174(51), 167(82), 45(68) 158 3,4-Cl₂—C₆H₃ i-C₃H₇ 4-F—C₆H₄ L 7.59˜6.87(m, 7H), 5.03˜4.84(m, 1H), 4.30(E) 4.16(Z) 467(20), 202(98), 167(100) (s, 2H), 1.09(d, 6H) 159 3,4-Cl₂—C₆H₃ i-C₃H₇ 3-Cl—C₆H₄ L 7.60˜6.92(m, 7H), 5.02˜4.82(m, 1H), 4.31(E) 4.15(Z) 483(42), 244(65), 204(100), (s, 2H), 1.08(d, 6H) 167(72) 160 3,4-Cl₂—C₆H₃ i-C₃H₇ 4-Cl—C₆H₄ 44˜45 7.70˜6.90(m, 7H), 5.02˜4.85(m, 1H), 4.30(E) 4.15(Z) 483(12), 244(39), 202(100), (s, 2H), 1.07(d, 6H) 167(54), 45(48) 161 3,4-Cl₂—C₆H₃ i-C₃H₇ 3,5-Cl₂—C₆H₃ 80˜81 7.61˜6.95(m, 6H), 5.05˜4.86(m, 1H), 4.28(E) 4.14(Z) 517(8), 202(99), 167(89), (s, 2H), 1.09(d, 6H) 45(100) 162 3-CH₃—C₆H₄ CH₃ C₅H₅ L 7.45˜6.90(m, 9H), 4.41(s, 2H), 3.27(s, 3H), 2.36(s, 3H) 367(15), 162(100), 147(34), 91(32) 163 3-CH₃—C₆H₄ CH₃ 4-CH₃—C₆H₄ 54 7.32˜6.90(m, 8H), 4.39(s, 2H), 3.26(s, 3H), 2.36(s, 3H), 381(13), 162(100), 147(37), 2.34(s, 3H) 91(34) 164 3-CH₃—C₆H₄ CH₃ 4-CH₃O—C₆H₄ 69 7.48˜6.79(m, 8H), 4.43(s, 2H), 3.82(s, 3H), 3.48(s, 3H), 397(15), 162(100), 134(42), 2.64(s, 3H) 91(42), 43(39) 165 3-CH₃—C₆H₄ CH₃ 4-F—C₆H₄ L 7.44˜6.93(m, 8H), 4.41(s, 2H), 3.27(s, 3H), 2.38(s, 3H) 385(16), 162(100), 147(60), 134(74), 91(65) 166 3-CH₃—C₆H₄ CH₃ 3-CF₃—C₆H₄ L 7.82˜6.98(m, 8H), 4.49(s, 2H), 3.28(s, 3H), 3.39(s, 3H) 435(25), 162(100), 147(69), 134(64), 91(69) 167 3-CH₃—C₆H₄ CH₃ 4-Cl—C₆H₄ L 7.40˜6.97(m, 8H), 4.42(s, 2H), 3.28(s, 3H), 2.39(s, 3H) 401(12), 162(100), 147(50), 134(56), 91(48) 168 4-CH₃—C₆H₄ CH₃ C₆H₄ 90 7.44˜6.99(m, 9H), 4.40(s, 2H), 326(s, 3H), 2.38(s, 3H) 367(15), 162(100), 147(48), 134(46), 91(47) 169 4-CH₃—C₆H₄ CH₃ 3-CH₃—C₆H₄ L 7.30˜6.99(m, 8H), 4.41(s, 2H), 3.27(s, 3H), 2.39(s, 3H), 381(14), 162(100), 147(46), 2.36(s, 3H) 134(36), 91(32) 170 4-CH₃—C₆H₄ CH₃ 4-CH₃—C₆H₄ 108 7.33˜6.99(m, 8H), 4.39(s, 2H), 3.28(s, 3H), 2.38(s, 3H), 381(13), 162(100), 147(41), 2.35(s, 3H) 134(36), 91(27) 171 4-CH₃—C₆H₄ CH₃ 4-CH₃O—C₆H₄ 83 7.36˜6.90(m, 8H), 4.38(s, 2H), 3.80(s, 3H), 3.28(s, 3H), 397(25), 162(100), 147(42), 2.37(s, 3H) 134(44), 91(43) 172 4-CH₃—C₆H₄ CH₃ 4-F—C₆H₄ 71 7.44˜6.69(m, 8H), 3.27(s, 3H), 2.38(s, 3H) 385(23), 162(100), 134(46), 91(26) 173 4-CH₃—C₆H₄ CH₃ 3-Cl—C₆H₄ L 7.43˜7.02(m, 8H), 4.42(s, 2H), 3.27(s, 3H), 2.38(s, 3H) 401(11), 162(100), 147(48), 134(38), 91(36) 174 4-CH₃—C₆H₄ CH₃ 3,5-Cl₂—C₆H₃ L 7.35˜7.04(m, 7H), 4.45(s, 2H), 3.28(s, 3H), 2.39(s, 3H) 435(15), 162(100), 147(54), 134(50) 175 4-CH₃—C₆H₄ CH₃ 4-C₆H₅O—C₆H₄ 80 7.40˜6.94(m, 13H), 4.35(s, 2H), 3.27(s, 3H), 2.39(s, 3H) 459(15), 162(100), 147(33), 134(28) 176 4-CH₃—C₆H₄ CH₃ 3,4-OCH₂O—C₆H₄ 68 7.26˜6.77(m, 7H), 5.95(s, 2H), 4.40(s, 2H), 3.27(s, 3H), 411(15), 162(100), 147(39), 2.38(s, 3H) 134(32) 177 3,4-(CH₃)₂—C₆H₃ CH₃ C₆H₅ L 7.45˜6.89(m, 8H), 4.42(s, 2H), 3.27(s, 3H), 2.28(s, 3H), 381(13), 161(33), 86(72), 2.27(s, 3H) 84(100) 178 3,4-(CH₃)₂—C₆H₃ CH₃ 4-C₂H₅—C₆H₄ L 7.34˜6.90(m, 7H), 4.41(s, 2H), 3.25(s, 3H), 2.30(s, 3H), 395(12), 176(100), 161(96), 2.28(s, 3H), 2.26(s, 3H) 43(49) 179 3,4-(CH₃)₂—C₆H₃ CH₃ 3,5-(CH₃)₂—C₆H₃ L 7.24˜6.86(m, 6H), 4.37(s, 2H), 3.22(s, 3H), 2.28(s, 6H), 409(19), 176(100), 161(65) 2.25(s, 3H), 2.31(s, 3H) 180 3,4-(CH₃)₂—C₆H₃ CH₃ 4-C₂H₅—C₆H₄ L 7.37˜6.88(m, 7H), 4.41(s, 2H), 3.26(s, 3H), 2.65(q, 2H), 409(24), 176(100), 161(58) 2.30(s, 3H), 2.28(s, 3H), 1.26(t, 3H) 181 3,4-(CH₃)₂—C₆H₃ CH₃ 4-F—C₆H₄ L 7.43˜6.83(m, 7H), 4.41(s, 2H), 3.25(s, 3H), 2.26(s, 6H) 399(18), 176(100), 161(99), 132(22) 182 3,4-(CH₃)₂—C₆H₃ CH₃ 4-CF₃—C₆H₄ L 7.69˜6.86(m, 7H), 4.39(s, 2H), 3.27(s, 3H), 2.89(s, 3H), 449(61), 176(100), 161(84) 2.27(s, 3H) 183 3,4-(CH₃)₂—C₆H₃ CH₃ 3-Cl—C₆H₄ L 7.32˜6.81(m, 7H), 4.42(s, 2H), 3.26(s, 3H), 2.29(s, 3H), 415(12), 176(97), 161(100), 2.28(s, 3H) 84(42) 184 3,4-(CH₃)₂—C₆H₃ CH₃ 4-C₆H₅O—C₆H₄ L 7.40˜6.85(m, 12H), 4.42(s, 2H), 3.26(s, 3H), 2.28(s, 3H), 473(25), 176(100), 161(76) 2.27(s, 3H) 185 3,4-(CH₃)₂—C₆H₃ i-C₃H₇ C₆H₅ 65 7.46˜6.78(m, 8H), 4.96(m, 1H), 4.30(s, 2H), 2.31(s, 3H), 409(36), 204(41), 162(100), 2.29(s, 3H), 1.06(d, 6H) 134(40) 186 3,4-(CH₃)₂—C₆H₃ i-C₃H₇ 4-CH₃—C₆H₄ L 7.27˜6.77(m, 7H), 4.95(m, 1H), 4.24(s, 2H), 2.35(s, 3H), 423(48), 204(51), 162(100), 2.29(s, 3H), 2.27(s, 3H), 1.05(d, 6H) 134(33) 187 3,4-(CH₃)₂—C₆H₃ i-C₃H₇ 4-F—C₆H₄ 52 7.45˜6.78(m, 7H), 4.93(m, 1H), 4.25(s, 2H), 2.28(s, 3H), 427(14), 204(37), 162(100), 2.26(s, 3H), 1.06(d, 6H) 134(34) 188 3,4-(CH₃)₂—C₆H₃ i-C₃H₇ 3-Cl—C₆H₄ 58 7.43˜6.79(m, 7H), 4.94(m, 1H), 4.26(s, 2H), 2.29(s, 3H), 443(18), 204(33), 162(100), 2.27(s, 3H), 1.06(d, 6H) 134(35) 189 4-CH₃O—C₆H₄ CH₃ 4-F—C₆H₄ L 7.44˜6.90(m, 8H), 4.39(s, 2H), 3.82(s, 3H), 3.25(s, 3H) 401(18), 178(100), 147(66), 121(53) 190 3-Cl—C₆H₄ CH₃ C₆H₅ L 7.42˜7.03(m, 9H), 4.41(s, 2H), 3.29(s, 3H) 387(14), 182(51), 147(100), 118(20) 191 3-Cl—C₆H₄ CH₃ 3-CH₃—C₆H₄ L 7.43˜7.16(m, 8H), 4.34(s, 2H), 3.27(s, 3H), 2.35(s, 3H) 401(14), 182(47), 147(100), 118(20) 192 3-Cl—C₆H₄ CH₃ 3,4-(CH₃)₂—C₆H₃ L 7.41˜7.01(m, 7H), 4.39(s, 2H), 3.27(s, 3H), 2.25(s, 6H) 415(17), 182(64), 147(100) 193 3-Cl—C₆H₄ CH₃ 4-C₂H₅—C₆H₄ L 7.42˜7.02(m, 8H), 4.40(s, 2H), 3.26(s, 3H), 2.64(q, 2H), 415(21), 182(99), 147(100) 1.26(t, 3H) 194 3-Cl—C₆H₄ CH₃ 4-t-C₄H₉—C₆H₄ L 7.42˜7.02(m, 8H), 4.41(s, 2H), 3.28(s, 3H), 1.31(s, 9H) 443(18), 182(72), 147(100) 195 3-Cl—C₆H₄ CH₃ 4-CH₃O—C₆H₄ L 7.43˜6.87(m, 8H), 4.40(s, 2H), 3.81(s, 3H), 3.29(s, 3H) 417(15), 182(52), 147(100), 78(19) 196 3-Cl—C₆H₄ CH₃ 3-F—C₆H₄ L 7.43˜7.02(m, 8H), 4.44(s, 2H), 3.30(s, 3H) 405(17), 182(38), 147(100) 197 3-Cl—C₆H₄ CH₃ 4-F—C₆H₄ L 7.43˜7.00(m, 8H), 4.36(s, 2H), 3.29(s, 3H) 405(30), 147(46), 85(60), 84(100), 43(51) 198 3-Cl—C₆H₄ CH₃ 4-Cl—C₆H₄ L 7.42˜7.06(m, 8H), 4.43(s, 2H), 3.28(s, 3H) 421(13), 182(40), 147(100), 43(26) 199 4-Cl—C₆H₄ CH₃ C₆H₅ 95 7.46˜7.09(m, 9H), 4.39(s, 2H), 3.29(s, 3H) 387(10), 181(28), 147(100) 200 4-Cl—C₆H₄ CH₃ 3-CH₃—C₆H₄ 74 7.47˜7.05(m, 8H), 4.39(s, 2H), 3.25(s, 3H), 2.35(s, 3H) 401(19), 182(48), 147(100) 201 4-Cl—C₆H₄ CH₃ 4-CH₃—C₆H₄ 99 7.48˜7.06(m, 8H), 4.38(s, 2H), 3.26(s, 3H), 2.34(s, 3H) 401(18), 147(71), 84(100), 47(83) 202 4-Cl—C₆H₄ CH₃ 3,4-(CH₃)₂—C₆H₃ 76 7.43˜7.02(m, 7H), 4.35(s, 2H), 3.24(s, 3H), 2.22(s, 6H) 415(15), 182(59), 147(100) 203 4-Cl—C₆H₄ CH₃ 4-C₂H₅—C₆H₄ 85 7.46˜7.04(m, 8H), 4.38(s, 2H), 3.25(s, 3H), 2.64(q, 2H), 415(14), 182(47), 147(100), 1.22(t, 3H) 118(24) 204 4-Cl—C₆H₄ CH₃ 3-CH₃O—C₆H₄ L 7.43˜6.85(m, 8H), 4.40(s, 2H), 3.81(s, 3H), 3.26(s, 3H) 417(19), 182(23), 147(100) 205 4-Cl—C₆H₄ CH₃ 4-CH₃O—C₆H₄ 90 7.43˜6.86(m, 8H), 4.31(s, 2H), 3.80(s, 3H), 3.26(s, 3H) 417(16), 182(47), 147(100) 206 4-Cl—C₆H₄ CH₃ 3-F—C₆H₄ L 7.47˜7.01(m, 8H), 4.42(s, 2H), 3.28(s, 3H) 405(17), 182(42), 147(100) 207 4-Cl—C₆H₄ CH₃ 4-F—C₆H₄ 72 7.48˜7.00(m, 8H), 4.40(s, 2H), 3.26(s, 3H) 405(18), 182(77), 147(100) 208 4-Cl—C₆H₄ CH₃ 3-Cl—C₆H₄ L 7.47˜7.09(m, 8H), 4.41(s, 2H), 3.27(s, 3H) 421(15), 182(45), 147(100) 209 4-Cl—C₆H₄ CH₃ 4-Cl—C₆H₄ 66 7.47˜7.09(m, 8H), 4.41(s, 2H), 3.28(s, 3H) 421(18), 182(29), 147(100), 118(29) 210 4-Cl—C₆H₄ CH₃ thiophene-2-yl L 7.47˜6.99(m, 7H), 4.45(s, 2H), 3.28(s, 3H) 393(24), 182(62), 147(100) 211 C₆H₅ CH₃ C₆H₅ L 7.51˜7.04(m, 10H), 4.32(s, 2H), 3.28(s, 3H) 403(23), 147(100), 120(94), 91(40) 212 C₆H₅ C₂H₅ C₆H₅ L 7.49˜7.01(m, 10H), 4.28(s, 2H), 3.75(q, 2H), 1.10(t, 3H) 417(24), 162(100), 134(94), 106(71), 91(62), 77(57) 213 C₆H₅ n-C₃H₇ C₆H₅ L 7.50˜7.02(m, 10H), 4.21(s, 2H), 3.67(t, 2H), 167˜1.45 431(63), 180(65), 133(60), (m, 2H), 0.91(t, 3H) 106(100) 214 C₆H₅ i-C₃H₇ C₆H₅ L 7.51˜7.00(m, 10H), 4.98(m, 1H), 4.10(s, 2H), 1.09(d, 6H) 431(24), 176(62), 133(100), 120(49) 215 4-CH₃O—C₆H₄ C₂H₅ C₆H₅ L 7.46˜6.84(m, 9H), 4.19(s, 2H), 3.81(s, 3H), 3.71(q, 2H), 447(55), 324(53), 239(52), 1.11(t, 3H) 149(100), 135(55), 120(41) 216 4-CH₃O—C₆H₄ n-C₃H₇ C₆H₅ L 7.47˜6.87(m, 9H), 4.26(s, 2H), 3.82(s, 3H), 3.65(t, 2H), 461(43), 206(100), 136(37), 1.67˜1.45(m, 2H), 0.90(t, 3H) 121(54) 217 3-CF₃—C₆H₄ i-C₃H₇ C₆H₅ L 7.76˜7.16(m, 9H), 4.94(m, 1H), 4.08(s, 2H), 1.08(d, 6H) 499(50), 244(46), 202(100), 174(66), 145(26), 43(74) 218 4-F—C₆H₄ i-C₃H₇ C₆H₅ L 7.46˜6.97(m, 9H), 4.97(m, 1H), 4.15(s, 2H), 1.02(d, 6H) 449(21), 194(33), 152(100), 124(45) 219 4-Cl—C₆H₄ C₂H₅ C₆H₅ L 7.49˜7.01(m, 9H), 4.20(s, 2H), 3.74(q, 2H), 1.10(t, 3H) 451(57), 324(47), 219(52), 182(78), 154(100), 139(42) 220 2,4-Cl₂—C₆H₄ CH₃ C₆H₅ L 7.54˜7.01(m, 8H), 4.20(s, 2H), 3.21(s, 3H) 471(41), 436(73), 181(100)

EXAMPLE 221 Preparation of N-2-(2′-Fluoro-1′-trifluoromethylstyryl-2′-oxy)acetylpiperidine (Compound 221)

The procedure of Example 1 was repeated except that 286 mg(2 mmol) of N-2-hydroxyacetylpiperidine obtained in Preparation 32 and 2,2-difluoro-1-trifluoromethyl styrene obtained in Preparation 56 were used and that silica gel column chromatography was conducted using a mixture of n-hexane and ethyl acetate(2:1) as an eluent to obtain 600 mg(yield 90.6%) of the title compound as a white solid.

¹H-NMR (CDCl₃, TMS) δ: 7.58-7.17(m, 5H), 4.79(E isomer) 4.67(Z isomer)(s, 2H), 3.17-3.05(m, 4H), 1.78-1.35(m, 6H); MS (m/e): 331(M⁺, 40), 126(85), 98(76), 84(100); ¹⁹F-NMR (CDCl₃, CFCl₃) δ: −57.38(Z isomer) −57.83(E isomer)(d,3F), −82.24(E isomer) −84.28(Z isomer)(q, 1F); m.p.: 78-79° C.

EXAMPLES 222 to 294

Using each of the alcoholic compounds obtained in Preparations 32 to 48 and each of the fluorovinyl compounds obtained in Preparations 49 to 56 and 58 to 65, the procedure of Example 221 was repeated to obtain 73 compounds(Compounds 222 to 294) of formula (I) of the present invention having various R¹, R² and R³ groups listed in Table 5. The ¹H-NMR and MS data and melting points of these compounds are also shown in Table 5. L in Table 5 represents liquid.

TABLE 5 (I)

R⁴ = CF₃ Comp. No. R¹ R² R³ state (° C.) NMR (CDCl₃, TMS) δ (ppm) MS (m/e) 221 —(CH₂)₅— C₆H₅ 78˜79 7.58˜7.17(m, 5H), 4.79(E) 4.67(Z) (s, 2H), 3.71˜3.05 331(40), 126(85), 98(76), (m, 4H), 1.78˜1.35(m, 6H) 84(100) 222 —(CH₂)₅— 3-CH₃—C₆H₄ L 7.31˜7.04(m, 4H), 4.78(E) 4.66(Z) (s, 2H), 3.64˜3.03 345(26), 126(71), 98(70), (m, 4H), 2.37(s, 3H), 1.74˜1.38(m, 6H) 84(100) 223 —(CH₂)₅— 4-CH₃—C₆H₄ L 7.43˜7.02(m, 4H), 4.79(E) 4.67(Z) (s, 2H), 3.64˜3.01 345(23), 326(18), 126(34), (m, 4H), 2.43(s, 3H), 1.98˜1.17(m, 6H) 98(100), 84(94) 224 —(CH₂)₅— 4-C₂H₅—C₆H₄ L 7.41˜7.13(m, 4H), 4.77(E) 4.68(Z) (s, 2H), 3.61˜3.06 359(11), 126(100), 98(51), (m, 4H), 2.64(q, 2H), 1.72˜1.38(m, 6H), 1.25(t, 3H) 84(61) 225 —(CH₂)₅— 3,4-(CH₃)₂—C₆H₃ L 7.21˜7.00(m, 3H), 4.79(E) 4.67(Z) (s, 2H), 3.60˜3.04 359(36), 126(85), 98(41), (m, 4H), 2.23(s, 6H), 1.70˜1.37(m, 6H) 84(100), 42(30) 226 —(CH₂)₅— 3,5-(CH₃)₂—C₆H₃ L 7.03˜6.87(m, 3H), 4.78(E) 4.66(Z) (s, 2H), 3.59˜3.01 359(40), 126(55), 98(63), (m, 4H), 2.26(s, 6H), 1.69˜1.34(m, 6H) 84(100), 42(57) 227 —(CH₂)₅— 3-CH₃O—C₆H₄ L 7.48˜6.72(m, 4H), 4.78(E) 4.66(Z) (s, 2H), 3.82(s, 3H), 361(23), 126(33), 98(83), 3.78˜2.98(m, 4H), 1.82˜1.43(m, 6H) 84(100) 228 —(CH₂)₅— 4-CH₃O—C₆H₄ L 7.52˜6.75(m, 4H), 4.79(E) 4.66(Z) (s, 2H), 3.84(s, 3H), 361(50), 157(44), 126(100) 3.78˜3.01(m, 4H), 1.84˜1.36(m, 6H) 98(92), 84(78), 55(69) 229 —(CH₂)₅— 3,4-OCH₂O—C₆H₃ L 6.94˜6.75(m, 3H), 5.94(s, 2H), 4.78(E) 4.65(Z) (s, 2H), 375(50), 126(53), 98(60), 3.63˜3.00(m, 4H), 1.70˜1.44(m, 6H) 84(100), 43(90) 230 —(CH₂)₅— 3-CF₃—C₆H₄ L 7.72˜7.32(m, 4H), 4.79(E) 4.65(Z) (s, 2H), 3.74˜3.02 399(87), 212(47), 127(100) (m, 4H), 1.97˜1.18(m, 6H) 231 —(CH₂)₅— 3-F—C₆H₄ L 7.62˜6.89(m, 4H), 4.80(E) 4.68(Z) (s, 2H), 3.75˜3.04 349(47), 126(64), 98(100), (m, 4H), 1.78˜0.94(m, 6H) 84(78) 232 —(CH₂)₅— 4-F—C₆H₄ L 7.51˜6.95(m, 4H), 4.79(E) 4.67(Z) (s, 2H), 3.62˜3.12 349(60), 126(66), 98(56), (m, 4H), 1.73˜1.45(m, 6H) 84(100), 42(55) 233 —(CH₂)₅— 3-Cl—C₆H₄ L 7.49˜7.17(m, 4H), 4.80(E) 4.67(Z) (s, 2H), 3.61˜3.07 365(35), 126(32), 98(20), (m, 4H), 1.72˜1.42(m, 6H) 84(100), 42(38) 234 —(CH₂)₅— 4-Cl—C₆H₄ L 7.78˜7.34(m, 4H), 4.79(E) 4.66(Z) (s, 2H), 3.85˜3.02 365(20), 126(57), 98(41), (m, 4H), 1.83˜1.42(m, 6H) 84(100), 45(69) 235 —(CH₂)₅— 3,5-Cl₂—C₆H₃ 54˜55 7.39˜7.15(m, 3H), 4.81(E) 4.70(Z) (s, 2H), 3.60˜3.08 399(41), 126(60), 98(42), (m, 4H), 1.78˜1.36(m, 6H) 84(100) 236 —(CH₂)₅— C₄H₃S-2-yl L 7.47˜6.94(m, 3H), 4.80(E) 4.70(Z) (s, 2H), 3.82˜3.07 337(10), 126(100), 98(74), (m, 4H), 1.81˜1.42(m, 6H) 84(80) 237 —CH(CH₃) (CH₂)₄— C₆H₅ L 7.63˜7.18(m, 5H), 4.83(E) 4.74(Z) (s, 2H), 3.25˜2.76 345(46), 140(52), 98(100), (m, 3H), 1.95˜1.48(m, 6H), 126(d, 3H) 84(46), 55(63) 238 —CH(CH₃) (CH₂)₄— 3-CH₃—C₆H₄ L 7.44˜6.92(m, 4H), 4.82(E) 4.75(Z) (s, 2H), 3.18˜2.72 359(65), 242(40), 98(78), (m, 3H), 2.35(s, 3H), 1.95˜1.46(m, 6H), 1.29(d, 3H) 84(92), 56(100) 239 —CH(CH₃) (CH₂)₄— 4-CH₃—C₆H₄ L 7.44˜7.03(m, 4H), 4.80(E) 4.74(Z) (s, 2H), 3.82˜2.45 359(15), 140(66), 98(100) (m, 3H), 2.42(s, 3H), 1.86˜1.42(m, 6H), 1.12(d, 3H) 240 —CH(CH₃) (CH₂)₄— 3,4-(CH₃)₂—C₆H₃ L 7.31˜7.03(m, 3H), 4.81(E) 4.74(Z) (s, 2H), 3.24˜2.75 373(30), 140(86), 98(100), (m, 3H), 2.28(s, 6H), 1.96˜1.45(m, 6H), 1.28(d, 3H) 55(75) 241 —CH(CH₃)(CH₂)₄— 3,5-(CH₃)₂—C₆H₃ L 7.28˜6.83(m, 3H), 4.80(E) 4.75(Z) (s, 2H), 3.25˜2.74 373(24), 140(89), 98(100), (m, 3H), 2.29(s, 6H), 1.96˜1.44(m, 6H), 1.26(d, 3H) 55(76) 242 —CH(CH₃)(CH₂)₄— 4-C₂H₅—C₆H₄ L 7.52˜7.05(m, 4H), 4.81(E) 4.76(Z) (s, 2H), 3.24˜2.85 373(45), 140(43), 98(100), (m, 3H), 2.71(q, 2H), 1.95˜1.45(m, 6H), 1.28(t, 3H), 55(43) 1.15(d, 3H) 243 —CH(CH₃)(CH₂)₄— 3-CH₃O—C₆H₄ L 7.47˜6.74(m, 4H), 4.79(E) 4.74(Z) (s, 2H), 3.78(s, 3H), 375(20), 140(97), 98(100), 3.24˜2.73(m, 3H), 1.95˜1.43(m, 6H), 1.24(d, 3H) 55(84) 244 —CH(CH₃)(CH₂)₄— 4-CH₃O—C₆H₄ L 7.54˜6.79(m, 4H), 4.80(E) 4.76(Z) (s, 2H), 3.87(s, 3H), 375(20), 140(56), 98(100), 3.22˜2.91(m, 3H), 1.97˜1.48(m, 6H), 1.33(d, 3H) 56(32) 245 —CH(CH₃)(CH₂)₄— 3,4-OCH₂O—C₆H₃ L 7.20˜6.62(m, 3H), 6.01(s, 2H), 4.79(E) 4.75(Z) (s, 2H), 389(19), 219(40), 140(87), 3.23˜2.74(m, 3H), 1.97˜1.49(m, 6H), 1.29(d, 3H) 112(74), 98(100), 55(77) 246 —CH(CH₃)(CH₂)₄— 3-CF₃—C₆H₄ L 7.76˜7.37(m, 4H), 4.78(E) 4.73(Z) (s, 2H), 3.25˜2.72 413(51), 140(29), 98(62), (m, 3H), 1.96˜1.42(m, 6H), 1.23(d, 3H) 84(69), 43(100) 247 —CH(CH₃)(CH₂)₄— 3-F—C₆H₄ L 7.53˜6.78(m, 4H), 4.79(E) 4.74(Z) (s, 2H), 3.24˜2.75 363(38), 140(38), 98(100), (m, 3H), 1.96˜1.46(m, 6H), 1.25(d, 3H) 55(45) 248 —CH(CH₃)(CH₂)₄— 4-F—C₆H₄ L 7.65˜6.82(m, 4H), 4.81(E) 4.75(Z) (s, 2H), 3.28˜2.65 363(50), 140(78), 112(46), (m, 3H), 1.95˜1.34(m, 6H), 1.16(d, 3H) 98(100), 55(57) 249 —CH(CH₃)(CH₂)₄— 3-Cl—C₆H₄ L 7.58˜7.28(m, 4H), 4.80(E) 4.75(Z) (s, 2H), 3.21˜2.94 379(72), 140(44), 98(100), (m, 3H), 1.98˜1.49(m, 6H), 1.32(d, 3H) 56(57) 250 —CH(CH₃)(CH₂)₄— 4-Cl—C₆H₄ L 7.57˜7.18(m, 4H), 4.81(E) 4.74(Z) (s, 2H), 3.18˜2.74 379(35), 140(70), 98(100), (m, 3H), 1.75˜1.35(m, 6H), 1.15(d, 3H) 55(47) 251 —CH(CH₃)(CH₂)₄— 3,5-Cl₂—C₅H₃ L 7.64˜7.18(m, 3H), 4.80(E) 4.75(Z) (s, 2H), 3.24˜2.75 413(35), 140(49), 98(100), (m, 3H), 1.95˜1.44(m, 6H), 1.23(d, 3H) 55(57) 252 —CH(CH₃)(CH₂)₄— C₄H₃S-2-yl L 7.45˜6.91(m, 3H), 4.79(E) 4.74(Z) (s, 2H), 3.26˜2.73 351(20), 140(65), 98(100), (m, 3H), 1.97˜1.41(m, 6H), 1.24(d, 3H) 55(66), 41(47) 253 —CH(C₂H₅)(CH₂)₄— C₆H₅ L 7.48˜7.22(m, 5H), 4.80(E) 4.75(Z) (s, 2H), 3.58˜2.62 359(18), 154(100), 126(58), (m, 3H), 1.81˜1.21(m, 8H), 0.83(t, 3H) 112(98) 254 —CH(C₂H₅)(CH₂)₄— 4-CH₃—C₆H₄ L 7.43˜7.02(m, 4H), 4.81(E) 4.76(Z) (s, 2H), 4.01˜2.52 373(30), 354(15), 154(43), (m, 3H), 2.41(s, 3H), 1.98˜1.12(m, 8H), 0.92(t, 3H) 112(100) 255 —CH(C₂H₅)(CH₂)₄— 3-Cl—C₆H₄ L 7.59˜7.15(m, 4H), 4.80(E) 4.75(Z) (s, 2H), 4.54˜3.91 393(71), 154(41), 112(100) (m, 2H), 3.43˜3.12(m, 3H), 1.95˜1.23(m, 6H), 97(38), 55(61) 1.04(t, 3H) 256 —CH(CH₃)(CH₂)₃CH(CH₃)— 4-CH₃—C₆H₄ L 7.49˜7.01(m, 4H), 4.80(E) 4.74(Z) (s, 2H), 4.54˜3.96 373(49), 354(21), 217(100) (m, 2H), 2.42(s, 3H), 1.98˜1.51(m, 6H), 1.42(d, 6H) 153(48), 69(21) 257 —CH(CH₃)(CH₂)₃CH(CH₃)— 3-Cl—C₆H₄ 58˜59 7.62˜7.18(m, 4H), 4.81(E) 4.75(2) (s, 2H), 3.75˜2.76 393(60), 154(30), 112(100) (m, 2H), 1.98˜1.48(m, 6H), 1.42(d, 6H) 69(45), 55(62) 258 —CH(CH₃)(CH₂)₃CH(CH₃)— 3,5-Cl₂—C₆H₃ 98˜99 7.45˜7.21(m, 3H), 4.80(E) 4.76(Z) (s, 2H), 3.78˜3.54 427(20), 154(60), 112(100) (m, 2H), 1.98˜1.47(m, 6H), 1.28(d, 6H) 69(64), 55(80) 259 —(CH₂)₂CH═CHCH₂— 4-CH₃—C₆H₄ L 7.51˜7.10(m, 4H), 5.92˜5.62(m, 2H), 4.81(E) 4.74(Z) 343(10), 324(48), 124(74), (s, 2H), 4.18˜3.32(m, 4H), 2.43(s 3H), 96(42), 82(100) 2.42˜1.91(m, 2H) 260 —(CH₂)₂O(CH₂)₂— C₆H₅ L 7.42˜7.23(m, 5H), 4.80(E) 4.75(Z) (s, 2H), 3.72˜3.10 333(10), 129(69), 102(100) (m, 8H) 87(30) 261 —(CH₂)₂O(CH₂)₂— 4-CH₃—C₆H₄ 75˜76 7.43˜7.02(m, 4H), 4.81(E) 4.76(Z) (s, 2H), 4.02˜3.10 347(15), 128(48), 100(100) (m, 8H), 2.41(s, 3H) 262 —(CH₂)₃C(C₆H₄)C— C₆H₅ 72˜73 7.45˜7.10(m, 9H), 4.80(E) 4.74(Z) (s, 2H), 3.79(t, 2H), 379(14), 360(15), 174(70), 2.70(t, 2H), 2.06˜1.87(m, 2H) 146(70), 118(100) 263 —(CH₂)₃C(C₄H₄)C— 4-CH₃—C₆H₄ L 7.49˜7.02(m, 8H), 4.81(E) 4.76(Z) (s, 2H), 3.78(t, 2H), 393(38), 374(28), 174(89), 2.71(t, 2H), 2.42(s, 3H), 2.05˜1.86(m, 2H) 146(96), 118(100) 264 —(CH₂)₆— C₆H₅ L 7.50˜7.25(m, 5H), 4.80(E) 4.75(Z) (s, 2H), 3.60˜3.10 345(16), 147(100), 112(46) (m, 4H), 1.81˜1.45(m, 8H) 99(26) 265 —(CH₂)₆— 3-CH₃—C₆H₄ L 7.38˜7.08(m, 4H), 4.81(E) 4.76(Z) (s, 2H), 3.60˜3.13 359(15), 140(44), 98(100), (m, 4H), 2.31(s, 3H), 1.78˜1.38(m, 8H) 43(63) 266 —(CH₂)₆— 4-CH₃—C₆H₄ L 7.40˜7.10(m, 4H), 4.80(E), 4.75(Z) (s, 2H), 3.61˜3.17 359(13), 140(56), 97(53), (m, 4H), 2.38(s, 3H), 1.81˜1.48(m, 8H) 55(53), 43(100) 267 —(CH₂)₆— 4-C₂H₃—C₆H₄ L 7.40˜7.12(m, 4H), 4.81(E) 4.75(Z) (s, 2H), 3.60˜3.15 373(23), 140(100), 98(54) (m, 4H), 2.65(q, 2H), 1.85˜1.48(m, 8H), 1.26(t, 3H) 268 —(CH₂)₆— 3,4-(CH₃)₂—C₆H₃ L 7.24˜7.02(m, 3H), 4.79(E) 4.74(Z) (s, 2H), 3.58˜3.11 373(71), 140(51), 98(100) (m, 4H), 2.32(s, 6H), 1.77˜1.41(m, 8H) 269 —(CH₂)₆— 3,5-(CH₃)₂—C₆H₃ L 7.06˜6.91(m, 3H), 4.80(E) 4.75(Z) (s, 2H), 3.60˜3.12 373(31), 140(39), 98(100), (m, 4H), 2.30(s, 6H), 1.80˜1.44(m, 8H) 42(39) 270 —(CH₂)₆— 3-CH₃O—C₆H₃ L 7.29˜6.76(m, 4H), 4.80(E) 4.75(Z) (s, 2H), 3.74(s, 3H), 375(53), 140(55), 98(100), 3.54˜3.10(m, 4H), 1.78˜1.42(m, 8H) 43(56) 271 —(CH₂)₆— 4-CH₃O—C₆H₄ L 7.38˜6.80(m, 4H), 4.79(E) 4.74(Z) (s, 2H), 3.76(s, 3H), 375(21), 140(29), 98(44), 3.58˜3.12(m, 4H), 1.81˜1.46(m, 8H) 59(38), 43(100) 272 —(CH₂)₆— 3,4-OCH₂O—C₆H₃ L 7.15˜6.78(m, 3H), 5.97(s, 2H), 4.80(E) 4.75(Z) (s, 2H), 389(13), 140(70), 98(100) 3.75˜3.14(m, 4H), 1.98˜1.32(m, 8H) 273 —(CH₂)₆— 3-F—C₆H₄ L 7.40˜6.98(m, 4H), 4.79(E) 4.74(Z) (s, 2H), 3.61˜3.16 363(51), 140(42), 98(100), (m, 4H), 1.81˜1.48(m, 8H) 55(54), 42(65) 274 —(CH₂)₆— 4-F—C₆H₄ L 7.50˜6.98(m, 4H), 4.80(E) 4.75(Z) (s, 2H), 3.60˜3.15 363(51), 140(45), 98(96), (m, 4H), 1.81˜1.46(m, 8H) 55(58), 42(100) 275 —(CH₂)₆— 3-Cl—C₆H₄ L 7.49˜7.18(m, 4H), 4.81(E) 4.74(Z) (s, 2H), 3.62˜3.20 379(55), 140(52), 98(93), (m, 4H), 1.82˜1.50(m, 8H) 55(73), 42(100) 276 —(CH₂)₆— 4-Cl—C₆H₄ L 7.50˜7.15(m, 4H), 4.80(E) 4.75(Z) (s, 2H), 3.61˜3.17 379(56), 140(51), 98(82), (m, 4H), 1.83˜1.43(m, 8H) 55(70), 42(100) 277 —(CH₂)₆— 3,5-Cl₂—C₆H₃ L 7.43˜7.16(m, 3H), 4.80(E) 4.75(Z) (s, 2H), 3.63˜3.18 413(45), 140(48), 98(100), (m, 4H), 1.86˜1.47(m, 8H) 42(53) 278 —(CH₂)₆— C₄H₃S-2-yl L 7.40˜6.94(m, 3H), 4.79(E) 4.75(Z) (s, 2H), 3.61˜3.13 351(11), 140(50), 98(100), (m, 4H), 1.82˜1.43(m, 8H) 55(31), 42(41) 279 C₂H₅ C₂H₅ C₆H₅ L 7.50˜7.21(m, 5H), 4.77(E) 4.64(Z) (s, 2H), 3.45(q, 411), 319(28), 114(88), 86(62), 1.15(t, 6H) 72(100) 280 C₂H₅ C₂H₅ 4-CH₃—C₆H₄ L 7.45˜6.98(m, 4H), 4.78(E) 4.65(Z) (s, 2H), 3.45(q, 4H), 333(39), 314(75), 219(100), 2.38(s, 3H), 1.10(t, 6H) 72(82) 281 n-C₃H₇ n-C₃H₇ 4-CH₃—C₆H₄ L 7.46˜6.97(m, 4H), 4.77(E) 4.65(Z) (s, 2H), 3.21(t, 4H), 361(43), 342(52), 261(100), 2.37(s, 3H), 1.98˜1.23(m, 4H), 0.91(t, 6H) 100(23), 69(58) 282 i-C₃H₇ i-C₃H₇ 4-CH₃—C₆H₄ 73˜74 7.45˜6.98(m, 4H), 4.78(E) 4.66(Z) (s, 2H), 3.82˜3.32 361(52), 342(40), 261(100), (m, 2H), 2.38(s, 3H), 1.38(d, 12H) 158(49) 283 CH₂═CHCH₂ CH₂═CHCH₂ C₆H₅ L 7.49˜7.19(m, 5H), 5.86˜5.59(m, 2H), 5.30˜5.02(m, 4H), 343(19), 138(92), 110(63), 4.79(E) 4.66(Z) (s, 2H), 4.10˜3.62(m, 4H) 55(100) 284 CH₂═CHCH₂ CH₂═CHCH₂ 4-CH₃—C₆H₄ L 7.51˜6.97(m, 4H), 5.89˜5.42(m, 2H), 5.39˜4.98(m, 4H), 357(40), 138(54), 55(100) 4.77(E) 4.65(Z) (s, 2H), 4.18˜3.48(m, 4H), 2.38(s, 3H) 285 CH₂═CHCH₂ CH₂═CHCH₂ 3-CH₃O—C₆H₄ L 7.51˜6.81(m, 4H), 6.10˜5.51(m, 2H), 5.49˜4.98(m, 4H), 373(66), 354(23), 138(41), 4.79(E) 4.66(Z) (s, 2H), 4.10˜3.62(m, 4H), 3.82(s, 3H) 56(100) 286 CH₂═CHCH₂ CH₂═CHCH₂ 3-CF₃—C₆H₄ L 7.89˜7.21(m, 4H), 5.94˜5.42(m, 2H), 5.39˜4.96(m, 4H), 411(69), 195(100), 138(80), 4.79(E) 4.65(Z) (s, 2H), 4.18˜3.48(m, 4H) 110(51) 287 CH₂═CHCH₂ CH₂═CHCH₂ C₄H₃S-2-yl L 7.50˜6.91(m, 3H), 6.11˜5.50(m, 2H), 5.50˜4.97(m, 4H), 349(13), 183(30), 138(100), 4.78(E) 4.66(Z) (s, 2H), 4.12˜3.61(m, 4H) 133(48) 288 n-C₄H₉ n-C₄H₉ 4-CH₃—C₆H₄ L 7.48˜6.97(m, 4H), 4.79(E) 4.66(Z) (s, 2H), 3.21(t, 4H), 389(42), 370(21), 203(100), 2.38(s, 3H), 1.82˜1.10(m, 8H), 0.94(t, 6H) 186(72), 69(48) 289 i-C₄H₉ i-C₄H₉ 4-CH₃—C₆H₄ L 7.45˜6.98(m, 4H), 4.79(E) 4.65(Z) (s, 2H), 2.83(d, 4H), 389(14), 170(17), 128(100), 2.37(s, 3H), 2.04˜1.37(m, 2H), 0.89(d, 12H) 72(34) 290 C₂H₅ (CH₃)₂CH C₆H₅ L 7.71˜7.28(m, 5H), 4.78(E) 4.64(Z) (s, 2H), 3.98˜3.63 333(12), 205(40), 128(62), (m, 1H), 3.12(q, 2H), 1.12(t, 3H), 1.10(d, 6H) 86(100), 57(71) 291 CH₃ n-C₄H₉ 4-CH₃—C₆H₄ L 7.44˜6.97(m, 4H), 4.79(E) 4.64(Z) (s, 2H), 3.35(t, 2H), 347(28), 328(16), 203(100), 2.82(s, 3H), 2.28(s, 3H), 1.45˜1.30(m, 4H), 0.98(t, 3H) 144(67), 69(21) 292 C₂H₅ n-C₄H₉ 4-CH₃—C₆H₄ L 7.45˜6.96(m, 4H), 4.79(E) 4.65(Z) (s, 2H), 3.40(t, 2H), 361(27), 342(12), 203(100), 3.21(q, 2H), 2.28(s, 3H), 1.46˜1.31(m, 4H), 1.10(t, 3H), 158(39), 69(13) 0.97(t, 3H) 293 CH₃ (C₆H₅)CH₂ C₆H₅ L 7.49˜7.01(m, 10H), 4.80(E) 4.66(Z) (s, 2H), 4.41(s, 2H), 367(32), 164(100), 93(54), 2.82(s, 3H) 47(98) 294 CH₃ (C₆H₅)CH₂ 4-CH₃—C₆H₄ L 7.48˜6.98(m, 9H), 4.81(E) 4.67(Z) (s, 2H), 4.43(s, 2H), 381(25), 162(68), 91(100), 2.84(s, 3H), 2.42(s, 3H) 44(28)

Herbicidal Activity Test

Herbicidal activity tests were conducted using test plants planted in screening pots as follows.

Each of screening pots, having the shape of a cube and a top surface area of 140 cm², was filled with a wet mixture of paddy soil and a suitable amount of fertilizer, and sowed thereto were 100 barnyardgrass seeds, 20 bulrush seeds, 50 monochoria seeds, 2 flat-sedge tubers and 2 arrow head tubers(see Table 6). Two rice plant seedlings at the 3-leaf stage were then transplanted thereto, followed by filling water to a depth of 3 cm and kept in a greenhouse for 2 days.

Added to each of the screening pots thus prepared was 4 ml of a 50% acetone solution containing 0.1% Tween-20 and a predetermined amount of each of the compounds listed in Tables 4 and 5 so that the amount of the compound applied would correspond to 4, 1, 0.25, 0.0625 or 0.015 kg/ha. Then, the pot was kept in a greenhouse for 2 to 3 weeks.

The herbicidal activity was determined according to the procedure of Table 7 which was described by Frans et al., In research methods in weed science, ed. by Camper, 29-70 (1986) and Cho, K. Y., Search Report by Korea Research Institute of Chemical Technology, 916 (1989))”. The results are shown in Table 8.

TABLE 6 Abbreviation Genus-species name General name ORYSA Oryza sativa L. Rice ECHOR Echinochlora crus-galli Barnyardgrass 8P. BEAUV. var. oryzicola OHWI SCPJU Scirpus juncoides ROXB Bulrush MOOVA Monochoria vaginalis Monochoria PRESL CYPSE Cyperus serotinus ROTTB Flat-sedge SAGPY Sagittaria pygmaea MIQ Arrow head

TABLE 7 General Score Description Rice Weed 0 no effect no damage no preventive effect 10 week week a slight damage a slight damage 20 medium that can be but no preventive 30 strong recovered; no effect significant in- fluence on the harvest 40 medium week a visible damage a significant pre- 50 medium that can be re- ventive effect 60 strong covered but would reduce the harvest 70 strong week a severe damage a practically high 80 medium that can not preventive effect, 90 strong be recovered, and eradication at and extinction a score of 80 at a score of or higher 80 or higher 100 complete total complete destruction eradication

TABLE 8 Comp. amount No. (kg/ha) ORYSA ECHOR SCPJU MOOVA CYPSE SAGPY 1 4.0000 90 100 100 100 100 100 1.0000 60 100 100 100 100 50 0.2500 10 100 10 90 40 50 0.0625 0 100 0 80 40 20 0.0156 0 60 0 40 10 0 2 1.0000 90 100 100 100 — 70 0.2500 40 100 70 90 — 60 0.0625 0 100 40 90 — 0 0.0156 0 100 20 90 — 0 0.0040 0 75 0 60 — 0 3 1.0000 80 100 100 100 — 70 0.2500 10 100 90 100 — 50 0.0625 0 100 70 80 — 20 0.0156 0 100 20 60 — 0 0.0040 0 60 0 20 — 0 4 1.0000 70 100 70 100 100 20 0.2500 10 100 70 100 100 0 0.0625 0 100 70 100 80 0 0.0156 0 100 50 100 0 0 0.0040 0 20 0 0 0 0 5 1.0000 20 100 100 100 100 60 0.2500 10 100 30 100 100 0 0.0625 0 100 0 100 0 0 0.0156 0 95 0 90 0 0 0.0040 0 50 0 10 0 0 6 1.0000 20 100 100 100 100 60 0.2500 0 100 0 90 100 0.0625 0 95 0 50 0 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 7 1.0000 10 100 100 100 — 30 0.2500 0 100 100 100 — 30 0.0625 0 80 30 70 — 10 0.0156 0 60 0 40 — 0 0.0040 0 0 0 0 — 0 8 1.0000 0 100 20 90 30 70 0.2500 0 100 0 90 30 0 0.0625 0 95 0 0 10 0 0.0156 0 30 0 0 0 0 0.0040 0 0 0 0 0 0 9 4.0000 80 100 100 100 0 100 1.0000 50 100 60 100 0 60 0.2500 30 100 0 100 0 40 0.0625 0 100 0 100 0 0 0.0156 0 100 0 100 0 0 10 1.0000 20 100 100 100 100 0 0.2500 10 100 40 70 100 0 0.0625 0 100 0 30 10 0 0.0156 0 50 0 0 0 0 0.0040 0 0 0 0 0 0 11 4.0000 60 100 100 100 100 80 1.0000 10 100 100 100 100 50 0.2500 0 100 30 90 100 10 0.0625 0 90 10 60 100 0 0.0156 0 60 0 0 0 0 12 1.0000 0 100 100 100 100 50 0.2500 0 100 10 90 100 0 0.0625 0 100 0 60 10 0 0.0156 0 60 0 0 0 0 0.0040 0 0 0 0 0 0 13 4.0000 40 100 70 100 0 100 1.0000 30 100 40 100 0 100 0.2500 0 100 0 100 0 100 0.0625 0 95 0 80 0 100 0.0156 0 70 0 40 0 0 14 1.0000 50 100 100 100 100 70 0.2500 10 100 40 90 100 20 0.0625 0 100 20 70 50 0 0.0156 0 80 0 20 0 0 0.0040 0 50 0 0 0 0 15 1.0000 60 100 100 100 100 100 0.2500 0 100 30 100 100 30 0.0625 0 100 0 90 100 20 0.0156 0 90 0 30 20 0 0.0040 0 70 0 0 0 16 1.0000 30 100 100 100 100 50 0.2500 10 100 50 100 50 0.0625 0 100 50 100 0 0 0.0156 0 40 0 0 0 0 0.0040 0 0 0 0 0 0 17 1.0000 30 100 20 100 100 20 0.2500 10 100 0 100 100 20 0.0625 0 100 0 100 100 20 0.0156 0 90 0 100 40 0 0.0040 0 20 0 0 0 0 18 4.0000 0 100 30 90 50 20 1.0000 0 100 70 90 0 — 0.2500 0 70 40 80 0 0 0.0625 0 10 0 0 0 0 0.0156 0 0 0 0 0 0 19 4.0000 50 100 100 100 — 100 1.0000 40 100 100 100 — 100 0.2500 40 100 70 100 — 0 0.0625 20 95 — 100 — 0 0.0156 0 70 0 40 — 0 20 4.0000 60 100 100 100 100 70 1.0000 30 100 100 100 100 50 0.2500 10 100 10 90 30 0 0.0625 0 100 0 80 20 0 0.0156 0 60 0 30 0 0 21 1.0000 45 100 80 100 100 10 0.2500 10 100 40 100 100 0 0.0625 0 95 10 60 0 0 0.0156 0 60 0 0 0 0 0.0040 0 30 0 0 0 0 22 4.0000 20 100 50 100 100 0 1.0000 0 100 30 100 100 0 0.2500 0 100 30 90 20 0 0.0625 0 100 30 60 0 0 0.0156 0 60 0 40 0 0 23 1.0000 30 100 0 90 60 70 0.2500 0 100 0 70 0 0 0.0625 0 95 0 50 0 0 0.0156 0 40 0 0 0 0 0.0040 0 0 0 0 0 0 24 1.0000 30 100 40 100 0 0 0.2500 10 100 20 70 0 0 0.0625 0 90 0 50 0 0 0.0156 0 30 0 0 0 0 0.0040 0 10 0 0 0 0 25 1.0000 10 100 40 100 100 50 0.2500 0 90 0 50 100 0 0.0625 0 80 0 0 100 0 0.0156 0 70 0 0 0 0 0.0040 0 0 0 0 0 0 26 1.0000 40 100 50 90 0 0 0.2500 10 100 40 90 0 0 0.0625 0 95 30 70 0 0 0.0156 0 70 20 50 0 0 0.0040 0 0 0 20 0 0 27 1.0000 20 100 20 100 100 10 0.2500 10 100 0 90 50 0 0.0625 0 80 0 30 30 0 0.0156 0 10 0 0 0 0 0.0040 0 0 0 0 0 0 28 1.0000 20 100 10 100 100 30 0.2500 0 100 0 100 0 0 0.0625 0 100 0 100 0 0 0.0156 0 50 0 0 0 0 0.0040 0 0 0 0 0 0 30 1.0000 60 100 100 100 — 100 0.2500 50 100 100 100 — 60 0.0625 40 100 30 90 — 50 0.0156 0 80 10 70 — 0 0.4000 0 50 0 20 — 0 31 1.0000 40 100 80 100 — 30 0.2500 20 100 50 90 — 0 0.0625 0 95 0 80 — 0 0.0156 0 70 0 50 — 0 0.0040 0 10 0 0 — 0 32 1.0000 40 100 100 100 — 40 0.2500 30 100 100 100 — 20 0.0625 0 90 20 80 — 0 0.0156 0 60 0 20 — 0 0.0040 0 20 0 0 — 0 33 1.0000 20 100 50 100 — 30 0.2500 0 100 30 80 — 0 0.0625 0 80 0 70 — 0 0.0156 0 40 0 20 — 0 0.0040 0 0 0 0 — 0 34 1.0000 20 100 100 100 — 20 0.2500 10 100 80 100 — 10 0.0625 0 90 10 70 — 10 0.0156 0 70 0 50 — 0 0.0040 0 0 0 0 — 0 35 1.0000 20 100 100 100 — 50 0.2500 0 100 50 90 — 0 0.0625 0 80 30 70 — 0 0.0156 0 50 0 50 — 0 0.0040 0 10 0 20 — 0 36 1.0000 40 100 100 100 — 60 0.2500 0 100 20 90 — 60 0.0625 0 90 10 80 — 20 0.0156 0 60 0 50 — 0 0.0040 0 20 0 20 — 0 37 1.0000 70 100 100 100 — 70 0.2500 20 100 100 100 — 50 0.0625 0 100 50 90 — 30 0.0156 0 80 40 80 — 30 0.0040 0 50 20 40 — 0 38 1.0000 20 100 70 100 — 30 0.2500 10 100 60 100 — 30 0.0625 0 80 30 80 — 0 0.0156 0 20 0 40 — 0 0.0040 0 0 0 0 — 0 39 1.0000 10 100 70 100 — 10 0.2506 0 100 10 100 — 0.0625 0 80 0 70 — 0 0.0156 0 50 0 50 — 0 0.0040 0 50 0 20 — 0 40 1.0000 0 80 30 100 — 10 0.2500 0 70 30 100 — 0 0.0625 0 30 0 30 — 0 0.0156 0 0 0 30 — 0 0.0040 0 0 0 0 — 0 42 1.0000 0 100 30 100 30 20 0.2500 0 100 30 100 30 20 0.0625 0 80 0 80 0 0 0.0156 0 80 0 50 0 0 0.0040 0 10 0 0 0 0 43 1.0000 0 100 0 90 100 0 0.2500 0 100 0 80 30 0 0.0625 0 95 0 40 10 0 0.0156 0 70 0 20 0 0 0.0040 0 0 0 0 0 0 44 4.0000 70 100 90 100 100 100 1.0000 60 100 50 100 100 100 0.2500 40 100 30 100 100 100 0.0625 20 100 0 70 80 50 0.0156 0 100 0 60 30 0 45 4.0000 50 100 70 100 100 100 1.0000 40 100 40 100 100 100 0.2500 30 100 0 90 100 100 0.0625 20 100 0 60 50 30 0.0156 0 100 0 60 0 0 46 4.0000 60 100 60 100 90 0 1.0000 20 100 50 100 0 0 0.2500 0 100 50 90 0 0 0.0625 0 95 30 70 0 0 0.0156 0 90 0 70 0 0 47 1.0000 10 100 30 90 90 50 0.2500 0 95 10 70 90 30 0.0625 0 80 0 30 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 48 4.0000 40 100 50 100 100 80 1.0000 30 100 40 90 60 0 0.2500 0 100 0 90 0 0 0.0625 0 100 0 50 0 0 0.0156 0 30 0 20 0 0 49 4.0000 90 100 100 100 0 50 1.0000 40 100 80 100 0 30 0.2500 0 100 70 100 0 0 0.0625 0 100 40 100 0 0 0.0156 0 95 20 50 0 0 50 1.0000 30 100 70 100 100 20 0.2500 20 100 10 90 100 0 0.0625 0 100 0 60 0 0 0.0156 0 95 0 20 0 0 0.0040 0 20 0 0 0 0 51 1.0000 20 100 30 100 100 0 0.2500 0 100 10 50 100 0 0.0625 0 100 0 20 0 0 0.0156 0 20 0 0 0 0 0.0040 0 0 0 0 0 0 52 4.0000 30 100 100 100 — 50 1.0000 20 100 50 100 — 0 0.2500 0 100 0 90 40 0 0.0625 0 70 0 50 30 0 0.0156 0 70 0 0 30 0 53 4.0000 20 100 30 100 100 30 1.0000 10 100 0 90 70 0 0.2500 0 100 0 80 50 0 0.0625 0 100 0 80 0 0 0.0156 0 40 0 30 0 0 54 4.0000 60 100 100 100 — 20 1.0000 0 100 50 100 — 0 0.2500 0 100 20 70 — 0 0.0625 0 100 0 70 — 0 0.0156 0 75 0 0 — 0 55 4.0000 40 100 100 100 100 90 1.0000 10 100 0 100 100 40 0.2500 0 100 0 80 20 20 0.0625 0 90 0 50 10 0 0.0156 0 60 0 0 0 0 56 4.0000 50 100 100 100 100 70 1.0000 10 100 10 100 100 0 0.2500 0 100 10 90 50 0 0.0625 0 100 10 70 0 0 0.0156 0 70 0 20 0 0 57 4.0000 0 100 0 100 100 0 1.0000 0 100 0 90 40 0 0.2500 0 80 0 50 0 0 0.0625 0 50 0 0 0 0 0.0156 0 0 0 0 0 0 58 4.0000 0 100 0 80 100 100 1.0000 0 100 0 70 100 100 0.2500 0 95 0 20 0 0 0.0625 0 60 0 0 0 0 0.0156 0 0 0 0 0 0 59 1.0000 0 100 20 40 100 10 0.2500 0 100 0 10 50 0 0.0625 0 10 0 0 0 0 0.0156 0 0 0 0 0 0 0.0040 0 0 0 0 0 0 60 4.0000 40 100 0 100 50 60 1.0000 10 100 0 100 50 20 0.2500 0 100 0 70 30 0 0.0625 0 90 0 30 0 0 0.0156 0 80 0 0 0 0 61 4.0000 20 100 40 100 0 0 1.0000 0 100 0 100 0 0 0.2500 0 100 0 80 0 0 0.0625 0 100 0 40 0 0 0.0156 0 0 0 0 0 0 62 4.0000 30 100 100 100 100 80 1.0000 10 100 0 90 60 0 0.2500 0 100 0 70 30 0 0.0625 0 80 0 10 0 0 0.0156 0 60 0 0 0 0 63 4.0000 20 100 0 100 100 0 1.0000 0 100 0 100 80 0 0.2500 0 100 0 80 40 0 0.0625 0 100 0 50 0 0 0.0156 0 20 0 0 0 0 64 4.0000 50 100 0 100 100 30 1.0000 20 100 0 100 100 0 0.2500 0 100 0 70 100 0 0.0625 0 70 0 50 0 0 0.0156 0 30 0 30 0 0 65 4.0000 10 100 30 100 0 30 1.0000 0 100 10 80 0 0 0.2500 0 100 0 50 0 0 0.0625 0 60 0 10 0 0 0.0156 0 50 0 0 0 0 66 4.0000 0 100 30 100 40 0 1.0000 0 100 20 90 40 0 0.2500 0 100 0 70 0 0 0.0625 0 95 0 40 0 0 0.0156 0 0 0 0 0 0 67 4.0000 10 100 40 100 30 70 1.0000 0 100 0 100 20 0 0.2500 0 100 0 70 0 0 0.0625 0 60 0 0 0 0 0.0156 0 50 0 0 0 0 68 4.0000 0 100 40 100 80 20 1.0000 0 100 20 90 0 0 0.2500 0 100 0 70 0 0 0.0625 0 60 0 30 0 0 0.0156 0 20 0 0 0 0 69 4.0000 50 100 0 100 100 30 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0.0056 0 60 0 0 0 0 261 4.0000 100 100 100 100 100 90 1.0000 90 100 100 100 100 0 0.2500 20 90 90 60 100 0 0.0625 0 70 30 20 100 0 0.0156 0 0 0 0 0 0 262 2.0000 0 100 0 100 50 50 0.5000 0 100 0 100 20 0 0.1250 0 100 0 90 0 0 0.0310 0 60 0 30 0 0 0:0080 0 20 0 0 0 0 263 4.0000 0 100 20 100 100 50 1.0000 0 100 0 100 100 0 0.2500 0 100 0 100 100 0 0.0625 0 95 0 100 50 0 0.0156 0 80 0 30 0 0 264 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 90 0.2500 60 100 100 90 50 80 0.0625 10 100 100 90 30 30 0.0156 0 70 20 70 0 0 265 1.0000 50 100 100 100 — 80 0.2500 10 100 60 90 — 0 0.0625 0 95 10 90 — 0 0.0156 0 80 0 70 — 0 0.0040 0 20 0 60 — 0 266 1.0000 100 100 100 100 — 90 0.2500 0 100 90 90 — 60 0.0625 0 100 20 90 90 20 0.0156 0 70 10 80 0 0 0.0040 0 30 0 60 0 0 267 1.0000 10 100 50 90 — 80 0.2500 0 100 40 80 — 0 0.0625 0 95 30 80 70 0 0.0156 0 60 0 50 0 0 0.0040 0 0 0 0 0 0 268 1.0000 40 100 100 90 — 60 0.2500 0 100 90 90 — 40 0.0625 0 95 10 80 60 30 0.0156 0 65 0 70 0 0 0.0040 0 20 0 50 0 0 269 1.0000 70 100 90 100 — 80 0.2500 10 100 30 80 — 50 0.0625 0 95 0 80 — 10 0.0156 0 70 0 80 0 0 0.0040 0 0 0 40 0 0 270 1.0000 90 100 100 100 — 80 0.2500 50 100 30 90 — 50 0.0265 30 100 20 80 — 10 0.0156 10 70 10 80 0 0 0.0040 0 20 10 60 0 0 271 1.0000 10 100 90 90 — 80 0.2500 0 100 50 80 — 0 0.0625 0 90 10 70 60 0 0.0156 0 70 0 60 — 0 0.0040 0 0 0 50 0 0 272 1.0000 50 100 100 100 100 60 0.2500 0 100 30 80 20 0 0.0625 0 100 0 70 20 0 0.0156 0 70 0 20 0 0 0.0040 0 0 0 0 0 0 273 1.0000 50 100 100 100 — 90 0.2500 20 100 100 90 — 70 0.0625 0 100 30 90 60 20 0.0056 0 70 20 80 30 0 0.0040 0 30 0 30 30 0 274 1.0000 60 100 100 100 — 100 0.2500 0 100 100 100 — 90 0.0625 0 100 30 90 — 40 0.0156 0 80 30 80 80 0 0.0040 0 60 0 50 0 0 275 1.0000 20 100 100 100 — 70 0.2500 0 100 50 90 — 50 0.0625 0 90 10 80 50 10 0.0156 0 70 0 50 0 0 0.0040 0 0 0 30 0 0 276 1.0000 20 100 706 100 — 70 0.2500 0 100 30 90 — 20 0.0625 0 95 20 80 — 0 0.0156 0 75 0 50 — 0 0.0040 0 20 0 40 0 0 277 1.0000 20 100 10 100 0 50 02500 0 95 0 90 0 10 0.0625 0 30 0 70 0 0 0.0156 0 30 0 50 0 0 0.0040 0 0 0 0 0 0 278 1.0000 0 100 90 90 50 50 0.2500 0 80 70 90 — 0 0.0625 0 75 10 70 — 0 0.0156 0 50 0 50 0 0 0.0040 0 10 0 20 0 0 279 4.0000 90 100 100 100 100 100 1.0000 80 100 100 100 100 70 0.2500 10 100 90 80 100 50 0.0625 0 90 70 70 40 30 0.0156 0 60 0 30 0 0 280 4.0000 100 100 100 100 100 60 1.0000 40 100 100 90 100 50 0.2500 10 100 100 90 100 0 0.0625 0 90 30 30 0 0 0.0056 0 20 0 0 0 0 281 4.0000 40 100 100 100 70 0 1.0000 20 100 100 100 0 0 0.2500 0 90 0 40 0 0 0.0625 0 70 0 0 0 0 0.0156 0 20 0 0 0 0 282 4.0000 0 100 40 90 0 0 1.0000 0 100 0 50 0 0 0.2500 0 60 0 0 0 0 0.0625 0 40 0 0 0 0 0.0156 0 0 0 0 0 0 283 4.0000 70 100 100 100 100 0 1.0000 30 100 100 100 100 0 0.2500 0 100 50 100 100 0 0.0625 0 90 0 90 100 0 0.0156 0 90 0 20 10 0 284 4.0000 80 100 100 100 100 0 1.0000 40 100 100 100 100 0 0.2500 0 100 0 100 100 0 0.0625 0 80 0 80 100 0 0.0156 0 80 0 0 0 0 285 4.0000 80 100 100 100 100 100 1.0000 50 100 100 100 100 100 0.2500 40 100 90 90 100 100 0.0625 30 100 60 80 60 60 0.0156 0 60 0 50 0 0 286 4.0000 80 100 100 100 100 0 1.0000 40 100 40 100 100 0 0.2500 20 100 30 90 90 0 0.0625 0 80 20 80 20 0 0.0156 0 60 0 50 10 0 287 4.0000 60 100 100 100 100 100 1.0000 40 100 80 100 100 100 0.2500 30 100 40 100 50 100 0.0625 0 80 30 100 30 100 0.0156 0 80 0 60 30 50 288 4.0000 50 100 40 90 50 0 1.0000 0 100 0 40 0 0 0.2500 0 90 0 0 0 0 0..0625 0 50 0 0 0 0 0.0156 0 10 0 0 0 0 289 4.0000 0 80 0 40 100 60 1.0000 0.2500 0.0625 0.0156 290 4.0000 100 100 100 100 100 80 1.0000 40 100 100 100 100 80 0.2500 10 100 100 100 100 50 0.0625 0 100 50 70 40 0 0.0155 0 70 0 20 0 0 291 4.0000 100 100 100 100 100 0 1.0000 40 100 100 100 100 0 0.2500 10 100 0 100 100 0 0.0625 0 100 0 80 100 0 0.0156 0 80 0 0 0 0 292 4.0000 60 100 100 100 100 0 1.0000 30 100 100 100 100 0 0.2500 0 100 0 50 0 0 0.0625 0 95 0 0 0 0 0.0156 0 20 0 0 0 0 293 4.0000 70 100 100 100 100 90 1.0000 0 100 100 100 30 90 0.2500 0 100 100 100 30 0 0.0625 0 100 0 80 20 0 0.0156 0 50 0 20 0 0 294 4.0000 50 100 90 100 100 40 1.0000 20 100 60 100 20 — 0.2500 0 100 30 80 0 — 0.0625 0 80 0 80 0 0 0.0156 0 0 0 70 0 0

As can be seen from Table 8, the compounds of the present invention have high herbicidal activity against a wide spectrum of weeds and are very selective, e.g., they do not harm rice plants.

While the invention has been described with respect to the specific embodiments, it should be recognized that various modifications and changes may be made by those skilled in the art to the invention which also fall within the scope of the invention as defined by the appended claims. 

What is. claimed is:
 1. A compound of formula (I):

wherein: R¹ is a phenyl group optionally having one or more substituents selected from the group consisting of C₁₋₆ alkyl, halogen-substituted C₁₋₆ alkyl, C₁₋₆ alkoxy and halogen; R² is a C₁₋₆ alkyl group; or R¹ and R² together with the nitrogen atom to which they are bound form a 5-, 6- or 7-membered nitrogen heterocycle optionally having one or more ring oxygen atoms, double bonds and C₁₋₆ alkyl substituents; R³ is a phenyl or thiophen-2-yl group optionally having one or more substituents selected from the group consisting of C₁₋₆ alkyl, halogen-substituted C₁₋₆ alkyl, C₁₋₆ alkoxy, methylenedioxy and halogen; and R⁴ is a perfluoro C₁₋₆ alkyl group.
 2. The compound of claim 1, which is the E isomer of formula (I-a):


3. The compound of claim 1, which is the Z isomer of formula (I-b):


4. The compound of claim 1, wherein R¹ is phenyl group optionally having a halogen, methyl or methoxy substituent; R² is a methyl or i-propyl group; R³is a phenyl group optionally having a halogen or methoxy substituent; and R⁴ is CF₃ or CF₂CF₃.
 5. The compound of claim 1, wherein R¹ and R² together with the nitrogen atom to which they are bound form a piperidino, hexamethyleneimino, morphorino or 1,2,3,6-tetrahydropyridino ring optionally having one or two C₁₋₂ alkyl substituents, R³ is a phenyl group optionally substituted with a halogen or methoxy group and R⁴ is CF₃.
 6. A process for the preparation of the compound of claim 1 which comprises reacting a compound of formula (II) with a compound of formula (III) in the presence of a base:

wherein R¹, R², R³ and R⁴ have the same meanings as defined in claim
 1. 7. A herbicidal composition comprising a herbicidally effective amount of the compound of claim 1 as an active ingredient and an inert carrier. 